The nature of the electronic excited state of many symmetric multibranched donor–acceptor molecules varies from delocalized/multipolar to localized/dipolar depending on the environment. Solvent-driven localization breaks the symmetry and traps the exciton in one branch. Using a combination of ultrafast spectroscopies, we investigate how such excited-state symmetry breaking affects the photochemical reactivity of quadrupolar and octupolar A(-π-D)2,3 molecules with photoisomerizable A-π-D branches. Excited-state symmetry breaking is identified by monitoring several spectroscopic signatures of the multipolar delocalized exciton, including the S2←S1 electronic transition, whose energy reflects interbranch coupling. It occurs in all but nonpolar solvents. In polar media, it is rapidly followed by an alkyne-allene isomerization of the excited branch. In nonpolar solvents, slow and reversible isomerization corresponding to chemically-driven symmetry breaking, is observed. These findings reveal that the photoreactivity of large conjugated molecules can be tuned by controlling the localization of the excitation.
A significant number of quadrupolar dyes with a D-π-A-π-D or  A-π-D-π-A  structure, where D and A are electron donor and acceptor groups, were shown to undergo symmetry breaking (SB) upon optical excitation. During this process, electronic excitation, originally distributed evenly over the molecule, concentrates on one D−π–A branch, and the molecule becomes dipolar. This process can be monitored by time-resolved infrared spectroscopy and causes significant spectral dynamics. A theoretical model of excited-state SB developed earlier (Ivanov, A. I. J. Phys. Chem. C2018,122, 29165–29172) is extended to account for the temporal changes taking place in the IR spectrum upon SB. This model can reproduce the IR spectral dynamics observed in the -C≡C- stretching region with a D-π-A-π-D dye in two polar solvents using a single set of molecular parameters. This approach allows estimating the degree of asymmetry of the excited state in different solvents and its change during SB. Additionally, the relative contribution of different mechanisms responsible for the splitting of the symmetric and antisymmetric -C≡C-  stretching bands, which are both IR active upon SB, can be determined.
  • Halogen-Bond Assisted Photoinduced Electron Transfer
    B. Dereka, I. Fureraj, A. Rosspeintner and E. Vauthey
    Molecules, 24 (23) , 2019, p4361
    DOI:10.3390/molecules24234361 | Abstract | Article HTML | Article PDF
The formation of a halogen-bond (XB) complex in the excited state was recently reported with a quadrupolar acceptor–donor–acceptor dye in two iodine-based liquids (J. Phys. Chem. Lett. 2017, 8, 3927–3932). The ultrafast decay of this excited complex to the ground state was ascribed to an electron transfer quenching by the XB donors. We examined the mechanism of this process by investigating the quenching dynamics of the dye in the S1 state using the same two iodo-compounds diluted in inert solvents. The results were compared with those obtained with a non-halogenated electron acceptor, fumaronitrile. Whereas quenching by fumaronitrile was found to be diffusion controlled, that by the two XB compounds is slower, despite a larger driving force for electron transfer. A Smoluchowski–Collins–Kimball analysis of the excited-state population decays reveals that both the intrinsic quenching rate constant and the quenching radius are significantly smaller with the XB compounds. These results point to much stronger orientational constraint for quenching with the XB compounds, indicating that electron transfer occurs upon formation of the halogen bond.
  • Tuning symmetry breaking charge separation in perylene bichromophores by conformational control
    A. Aster, G. Licari, F. Zinna, E. Brun, T. Kumpulainen, E. Tajkhorshid, J. Lacour and E. Vauthey
    Chemical Science, 10 , 2019, p10629-19639
    DOI:10.1039/C9SC03913A | Abstract | Article HTML | Article PDF | Supporting Info
Understanding structure–property relationships in multichromophoric molecular architectures is a crucial step in establishing new design principles in organic electronics as well as to fully understand how nature exploits solar energy. Here, we study the excited state dynamics of three bichromophores consisting of two perylene chromophores linked to three different crown-ether backbones, using stationary and ultrafast electronic spectroscopy combined with molecular dynamics simulations. The conformational space available to the bichromophores depends on the structure and geometry of the crown-ether and can be significantly changed upon cation binding, strongly affecting the excited-state dynamics. We show that, depending on the conformational restrictions and the local environment, the nature of the excited state varies greatly, going from an excimer to a symmetry-broken charge separated state. These results can be rationalised in terms of a structure–property relationship that includes the effect of the local environment.
The excited-state dynamics of the radical anion of perylene (Pe) generated upon bimolecular photoinduced electron transfer (PET) with a donor was investigated using broadband pump–pump–probe spectroscopy. It was found to depend on the age of the anion, that is, on the time interval between the first pump pulse that triggers PET and the second one that excites the ensuing Pe anion (Pe•–). These differences, observed in acetonitrile but not in tetrahydrofuran, report on the evolution of the PET product from an ion pair to free ions. Two photoinduced charge recombination pathways of the ion pair to the neutral Pe*(S1) + donor state were identified: one occurring in a few picoseconds from Pe•–*(D1) and one taking place within 100–200 fs from Pe•–*(Dn>1). Both processes are sensitive to the interionic distance over different length scales and thus serve as molecular rulers.
  • Effect of symmetric and asymmetric substitution on the optoelectronic properties of 9,10-dicyanoanthracene
    F. Glcklhofer, A. Rosspeintner, P. Pasitsuparoad, S. Eder, J. Frhlich, G. Angulo, E. Vauthey and F. Plasser
    Mol. Sys. Des. Eng., 4 , 2019, p251-261
    DOI:10.1039/C9ME00040B | Abstract | Article HTML | Article PDF
The structural dynamics of an electron donor/acceptor complex (DAC) consisting of benzene and tetracyanoethylene (Bz/TCNE) solvated in CH2Cl2 have been investigated using ultrafast spectroscopy and mixed quantum/classical computer simulations. Population dynamics from visible and infrared transient absorption (TRIR) spectroscopy point to complex sub-10 ps dynamics followed by charge recombination on a 55 to 60 ps timescale. Structural dynamics involving large-scale reorganization of radical ion pairs are revealed using TRIR anisotropy measurements. A computational study combining quantum chemical calculations and classical molecular dynamics simulations was able to reproduce the experimental electronic absorption lineshape and TRIR anisotropy dynamics, allowing for a detailed investigation of the pair conformational dynamics. Contrary to the static single structure typically assumed in descriptions of DACs, we find that neither the ground nor excited state can be described using a single, well-defined species. Instead, the pair undergoes a rearrangement from disordered pi-stacks to edge-to-face T-shaped structures following excitation. Translational diffusion of the radical ion pairs following excitation was found to be heterogeneous and dependent on both pair separation and orientation coordinates. Given the sensitivity of charge-transfer reactions to the arrangement of donor/acceptor pairs, the structural heterogeneity and corresponding dynamics demonstrated herein must be taken into account in future modeling of charge recombination processes in DACs.
The influence of torsional disorder around the ethynyl pi-bridges of a linear D-pi-A-pi-D molecule on the nature of its S1 excited state was investigated using ultrafast time-resolved infrared spectroscopy. By tuning the pump wavelength throughout the S1<- S0 absorption band, subpopulations with different extents of asymmetry could be excited. In non-polar solvents, the equilibrated S1 state is symmetric and quadrupolar independently of the initial degree of distortion. Photoexcitation of distorted molecules is followed by planarization and symmetrization of the S1 state. Excited-state symmetry breaking is only observed in polar environments, where the equilibrated S1 state has a strong dipolar character. However, neither the extent nor the rate of symmetry breaking are enhanced in an initially distorted molecule. They are only determined by the polarity and the dynamic properties of the solvent.
  • Towards efficient initiators for two-photon induced polymerization: fine tuning of the donor/acceptor properties

    Mol. Sys. Des. Eng., 4 , 2019, p437-448
    DOI:10.1039/C8ME00101D | Abstract | Article HTML | Article PDF | Supporting Info
In this work we present the design, synthesis and systematic investigation of the optical properties of symmetric triphenylamine (TPA)-substituted thiophenes. The use of electron-donating (-OMe, -tBu, -Me, -TMS), -neutral (-H) or -withdrawing (-F, -CN, -SO2Me) substituents gives rise to D-A-D based two-photon absorption (2PA) chromophores. The photophysical properties of these compounds, including one-photon absorption and 2PA using two-photon-excited fluorescence, were investigated in different organic solvents with varying polarity. The maximum 2PA cross sections prove to be strongly dependent on the nature of the TPA substituent and range between  ca. 173 GM (Goeppert-Mayer units) and 379 GM. Although most of the investigated substances also exhibit high fluorescence quantum yields, two-photon absorption screening tests of an acrylate monomer formulation revealed the efficiency of these materials as 2PA photoinitiators. These results are supported by quantum chemical calculations of the spin density distribution indicating that the mechanism of polymerization initiation using acrylate monomer is favored by strong localization of the unpaired electrons in the triplet state on the C2 carbon of the thiophene moiety.
The dynamics of the ion pairs produced upon fluorescence quenching of the electron donor 9,10-dimethylanthracene (DMeA) by phthalonitrile have been investigated in acetonitrile and tetrahydrofuran using transient absorption spectroscopy. Charge recombination to both the neutral ground state and the triplet excited state of DMeA is observed in both solvents. The relative efficiency of the triplet recombination pathway decreases substantially in the presence of an external magnetic field. These results were analyzed theoretically within the differential encounter theory, with the spin conversion of the geminate ion pairs described as a coherent process driven by the hyperfine interaction. The early temporal evolution of ion pair and triplet state populations with and without magnetic field could be well reproduced in acetonitrile, but not in tetrahydrofuran where fluorescence quenching involves the formation of an exciplex. A description of the spin conversion in terms of rates, i.e., incoherent spin transitions, leads to an overestimation of the magnetic field effect.
Intermolecular H‐bonding dynamics around a photoexcited quadrupolar dye is directly observed using transient 2D‐IR spectroscopy. Upon solvent‐induced symmetry breaking, the H‐bond accepting abilities of the two nitrile end‐groups change drastically, and in extremely protic (superprotic) solvents, a tight H‐bond complex forms at one end. The time evolution of the 2D C≡N lineshape in methanol points to rapid, 2–3 ps, spectral diffusion due to fluctuations of the H‐bonding network. Similar behavior is observed in a superprotic solvent shortly after photoexcitation of the dye. However, at later times, the completely inhomogeneous band does not exhibit spectral diffusion for at least 5 ps, pointing to a glass‐like environment around one side of the dye. About half of the excited dyes show this behavior attributed to the tight H‐bond complex, whereas the others are loosely bound. A weak cross peak indicates partial exchange between these excited state subpopulations.
  • Machine Learning for Analysis of Time-Resolved Luminescence Data
    N. Dordevic, J.S. Beckwith, M. Yarema, O. Yarema, A. Rosspeintner, N. Yazdani, J. Leuthold, E. Vauthey and V. Wood
    ACS Photonics, 5 (12) , 2018, p4888-4895
    DOI:10.1021/acsphotonics.8b01047 | Abstract | Article HTML | Article PDF | Supporting Info
Time-resolved photoluminescence is one of the most standard techniques to understand and systematically optimize the performance of optical materials and optoelectronic devices. Here, we present a machine learning code to analyze time-resolved photoluminescence data and determine the decay rate distribution of an arbitrary emitter without any a priori assumptions. To demonstrate and validate our approach, we analyze computer-generated time-resolved photoluminescence data sets and show its benefits for studying the photoluminescence of novel semiconductor nanocrystals (quantum dots), where it quickly provides insight into the possible physical mechanisms of luminescence without the need for educated guessing and fitting.
The excited-state dynamics of a T-shaped bichromophoric molecule, consisting of two strong fluorophores, diphenyloxazole and diphenylpyrazoline, directly linked in an orthogonal geometry, was investigated. Despite the weak coupling ensured by this geometry and confirmed by the electronic absorption spectra, this dyad exhibits only weak fluorescence in both apolar and polar solvents, with fluorescence lifetimes ranging from 200 ps in CHX to 10 ps in ACN. Ultrafast spectroscopic measurements reveal that the fluorescence quenching in polar solvents is due to the population of a charge-separated state. In non-polar solvents, this process is energetically not feasible, and a quenching due to an efficient intersystem crossing (ISC) to the triplet manifold is proposed, based on quantum-chemical calculations. This process occurs via the spin–orbit charge-transfer (SOCT) ISC mechanism, which is enabled by the charge-transfer character acquired by the S1 state of the dyad upon structural relaxation and by the orthogonal arrangement of the molecular orbitals involved in the transition. The same mechanism is proposed to explain why the recombination of the charge-separated state is faster in medium than in highly polar solvents, as well as to account for the fast decay of the lowest triplet state to the ground state.
Bimolecular photoinduced electron transfer between perylene and two quenchers was investigated in an imidazolium room-temperature ionic liquid (RTIL) and in a dipolar solvent mixture of the same viscosity using transient absorption on the subpicosecond to submicrosecond time scales. Whereas charge separation dynamics were similar in both solvents, significant differences were observed in the temporal evolution of the ensuing radical ions: although small, the free-ion yield is significantly larger in the RTIL, and recombination of the ion pair to the triplet state of perylene is more efficient in the dipolar solvent. The temporal evolution of reactant, ion, and triplet state populations could be well reproduced using unified encounter theory. This analysis reveals that the observed differences can be explained by the strong screening of the Coulomb potential in the ion pair by the ionic solvent. In essence, RTILs favor free ions compared to highly dipolar solvents of the same viscosity.
  • Wavelength-optimized Two-Photon Polymerization Using Initiators Based on Multipolar Aminostyryl-1,3,5-triazines
    M. Tromayer, P. Gruber, A. Rosspeintner, A. Ajami, W. Husinsky, F. Plasser, L. Gonzlez, E. Vauthey, A. Ovsianikov and R. Liska
    Scientific Reports, 8 (1) , 2018, p17273
    DOI:10.1038/s41598-018-35301-x | Abstract | Article HTML
Two-photon induced polymerization (2PP) based 3D printing is a powerful microfabrication tool. Specialized two-photon initiators (2PIs) are critical components of the employed photosensitive polymerizable formulations. This work investigates the cooperative enhancement of two-photon absorption cross sections (σ2PA) in a series of 1,3,5-triazine-derivatives bearing 1-3 aminostyryl-donor arms, creating dipolar, quadrupolar and octupolar push-pull systems. The multipolar 2PIs were successfully prepared and characterized, σ2PA were determined using z-scan at 800 nm as well as spectrally resolved two-photon excited fluorescence measurements, and the results were compared to high-level ab initio computations. Modern tunable femtosecond lasers allow 2PP-processing at optimum wavelengths tailored to the absorption behavior of the 2PI. 2PP structuring tests revealed that while performance at 800 nm is similar, at their respective σ2PA-maxima the octupolar triazine-derivative outperforms a well-established ketone-based quadrupolar reference 2PI, with significantly lower fabrication threshold at exceedingly high writing speeds up to 200 mm/s and a broader window for ideal processing parameters.
  • Cyclopeptidic photosensitizer prodrugs as proteolytically triggered drug delivery systems of pheophorbide A: part II  co-loading of pheophorbide A and black hole quencher
    J. Bouilloux, O. Yuschenko, B. Dereka, G. Boso, A. Babic, H. Zbinden, E. Vauthey and N. Lange
    Photochemical & Photobiological Sciences, 17 (11) , 2018, p1739-1748
    DOI:10.1039/C8PP00318A | Abstract | Article HTML | Article PDF
Previously, we have shown that the use of a cyclopeptidic carrier could be of great interest for the design of fully characterized prodrugs for further use in photodynamic therapy. In order to further optimize the design, we decided to modify the highly quenched conjugate uPA-cPPP4/5 by co-loading a long-distance fluorescence quencher. For this purpose we tethered two black hole quenchers (BHQ3) together with two pheophorbide A moities onto the same PEGylated backbone and assessed the modified photophysical properties. In addition, to prove the reliability of our concept, we designed two analogues, uPA-cPPQ2+2/5 and CathB-cPPQ2+2/5, by using two different peptidic linkers as substrates for uPA and cathepsin B, respectively. These two conjugates proved to be much more water-soluble than their analogues bearing only Phas. These conjugates are not only highly quenched in their native state with regard to their fluorescence emission (up to 850 ± 287 times less fluorescent for CathB-cPPQ2+2/5 as compared to the unquenched monosubstituted reference uPA-cPPP1/5), but also prevent singlet oxygen production (with a total quenching of the emission when the quenchers are co-loaded with photosensitizers) when the photosentistizers are excited. After proteolytic activation, these conjugates recover their photophysical properties in the same way as occurred for uPA-cPPP4/5, with up to a 120-fold increase in fluorescence emission for uPA-cPPQ2+2/5 after two hours of incubation with uPA.
  • Cyclopeptidic photosensitizer prodrugs as proteolytically triggered drug delivery systems of pheophorbide A: part I self-quenched prodrugs
    J. Bouilloux, O. Yuschenko, B. Dereka, G. Boso, H. Zbinden, E. Vauthey, A. Babic and N. Lange
    Photochemical & Photobiological Sciences, 17 (11) , 2018, p1728-1738
    DOI:10.1039/C8PP00317C | Abstract | Article HTML | Article PDF
Herein, we report the synthesis of a new prodrug system consisting of regioselectively addressable functionalized templates bearing multiple pheophorbide A moieties for use in photodynamic therapy. These coupling reactions were achieved using copper-free “click” chemistry, namely a strain-promoted azide–alkyne cycloaddition. This new design was used to obtain well-defined quenched photosensitizer prodrugs with perfect knowledge of the number and position of loaded photosensitizers, providing structures bearing up to six photosentitizers and two PEG chains. These conjugates are ideally quenched in their native state regarding their fluorescence emission (up to 155 ± 28 times less fluorescent for an hexasubstituted conjugate than a monosubstituted non-quenched reference compound) or singlet oxygen production (decreased 8.7-fold in the best case) when excited. After 2 h of proteolytic activation, the fluorescence emission of a tetrasubstituted conjugate was increased 17-fold compared with the initial fluorescence emission.
  • Optical transient absorption experiments reveal the failure of formal kinetics in diffusion assisted electron transfer reactions
    G. Angulo, A. Rosspeintner, B. Lang and E. Vauthey
    Physical Chemistry Chemical Physics, 20 (39) , 2018, p25531-25546
    DOI:10.1039/C8CP05153D | Abstract | Article HTML | Article PDF
The ultimate goal of chemical kinetics is to understand why a given reaction is fast or not. To this end it is necessary to count on robust and experimentally well tested theories. One of the difficulties, long recognized in the study of bimolecular reactions, is the role of the molecular displacement, i.e. diffusion. Nonetheless the field is still lacking a compelling amount of case studies contrasting physical models to experiments. By performing transient absorption experiments on the photo-induced electron transfer reaction between perylene and N,N-dimethylaniline in liquid solutions over many orders of magnitude in time, we try to understand the factors determining the kinetics and yields of the full photocycle. We present a method to overcome potential pitfalls in the extraction of the relevant quantities, the transient populations, from the experimental data due to the changes in band shapes and positions. The results are compared to simulations of two different theories: a reaction–diffusion approach based on the encounter theories, and a formal kinetic scheme. We conclude that while the former explains the observed trends in the kinetics with quencher concentration and viscosity exceptionally well, the latter fails. Moreover the analysis of the data with the assistance of encounter theory unveils effects that otherwise would pass unnoticed. This approach and its results exemplify the path to follow in other condensed media whenever diffusion is involved.
  • White-Fluorescent Dual-Emission Mechanosensitive Membrane Probes that Function by Bending Rather than Twisting
    H.V. Humeniuk, A. Rosspeintner, G. Licari, V. Kilin, L. Bonacina, E. Vauthey, N. Sakai and S. Matile
    Angewandte Chemie International Edition, 57 (33) , 2018, p10559-10563
    DOI:10.1002/anie.201804662 | Abstract | Article HTML | Article PDF
Bent N,N′‐diphenyl‐dihydrodibenzo[a,c]phenazine amphiphiles are introduced as mechanosensitive membrane probes that operate by an unprecedented mechanism, namely, unbending in the excited state as opposed to the previously reported untwisting in the ground and twisting in the excited state. Their dual emission from bent or “closed” and planarized or “open” excited states is shown to discriminate between micelles in water and monomers in solid‐ordered (So), liquid‐disordered (Ld) and bulk membranes. The dual‐emission spectra cover enough of the visible range to produce vesicles that emit white light with ratiometrically encoded information. Strategies to improve the bent mechanophores with expanded π systems and auxochromes are reported, and compatibility with imaging of membrane domains in giant unilamellar vesicles by two‐photon excitation fluorescence (TPEF) microscopy is demonstrated.
  • Highly Stable and Red-Emitting Nanovesicles Incorporating Lipophilic Diketopyrrolopyrroles for Cell Imaging
    A. Ardizzone, D. Blasi, D. Vona, A. Rosspeintner, A. Punzi, E. Altamura, N. Grimaldi, S. Sala, E. Vauthey, G.M. Farinola, I. Ratera, N. Ventosa and J. Veciana
    Chemistry - A European Journal, 24 (44) , 2018, p11386-11392
    DOI:10.1002/chem.201801444 | Abstract | Article HTML | Article PDF
Diketopyrrolopyrroles (DPPs) have recently attracted much interest as very bright and photostable red‐emitting molecules. However, their tendency to form nonfluorescent aggregates in water through the aggregation‐caused quenching (ACQ) effect is a major issue that limits their application under the microscope. Herein, two DPP molecules have been incorporated into the membrane of highly stable and water‐soluble quatsomes (QS; nanovesicles composed of surfactants and sterols), which allow their nanostructuration in water and, at the same time, limits the ACQ effect. The obtained fluorescent organic nanoparticles showed superior structural homogeneity, along with long‐term colloidal and optical stability. A thorough one‐ (1P) and two‐photon (2P) fluorescence characterization revealed the promising photophysical features of these fluorescent nanovesicles, which showed a high 1P and 2P brightness. Finally, the fluorescent QSs were used for the in vitro bioimaging of Saos‐2 osteosarcoma cell lines; this demonstrates their potential as nanomaterials for bioimaging applications.
  • Ultrafast excited state decay of natural UV filters: from intermolecular hydrogen bonds to a conical intersection
    P.S. Sherin, Y.P. Tsentalovich, E. Vauthey and E. Benassi
    Physical Chemistry Chemical Physics, 20 (22) , 2018, p15074-15085
    DOI:10.1039/C8CP02183J | Abstract | Article HTML | Article PDF
Kynurenines (KNs) are natural UV filters of the human eye lens, protecting the eye tissues from solar UV radiation. Key points of their effective protection are the intramolecular charge transfer (ICT) in the excited state and the fast dissipation of absorbed light energy into heat via the intermolecular H-bonds. Herein we report that the introduction of an unsaturated double bond in the amino acid side chain, operating as an ICT-enhancing electron donor group, drastically accelerates the internal conversion (IC) due to a conical intersection (CI) between the potential energy surfaces of the excited and ground states. Our photophysical study of a deaminated KN (carboxyketoalkene, CKA), an intrinsic product of KN thermal decomposition, demonstrates an unusually fast excited state decay in a broad range of solvents of different polarity and proticity. The detailed analysis of interactions in the excited state by different computational techniques revealed that the changes in molecular structure – the twist of the carbonyl group from the plane of the aromatic ring followed by the formation of two mutually orthogonal conjugated substructures – are responsible for the CI of the excited and ground state potential energy surfaces. Intermolecular H-bonds facilitate the transition to the CI, but do not play a crucial role in the fast decay of the excited state. An extremely fast and efficient IC in CKA opens the way for the design of new types of organic UV filters and their applications in material science, cosmetics and medicine.
In this report, we demonstrate that synergistic effects between π–π stacking and anion−π interactions in π-stacked foldamers provide access to unprecedented catalytic activity. To elaborate on anion–(π)n–π catalysis, we have designed, synthesized and evaluated a series of novel covalent oligomers with up to four face-to-face stacked naphthalenediimides (NDIs). NMR analysis including DOSY confirms folding into π stacks, cyclic voltammetry, steady-state and transient absorption spectroscopy the electronic communication within the π stacks. Catalytic activity, assessed by chemoselective catalysis of the intrinsically disfavored but biologically relevant addition reaction of malonate half thioesters to enolate acceptors, increases linearly with the length of the stacks to reach values that are otherwise beyond reach. This linear increase violates the sublinear power laws of oligomer chemistry. The comparison of catalytic activity with ratiometric changes in absorption and decreasing energy of the LUMO thus results in superlinearity, that is synergistic amplification of anion−π catalysis by remote control over the entire stack. In computational models, increasing length of the π-stacked foldamers correlates sublinearly with changes in surface potentials, chloride binding energies, and the distances between chloride and π surface and within the π stack. Computational evidence is presented that the selective acceleration of disfavored but relevant enolate chemistry by anion−π catalysis indeed originates from the discrimination of planar and bent tautomers with delocalized and localized charges, respectively, on π-acidic surfaces. Computed binding energies of keto and enol intermediates of the addition reaction as well as their difference increase with increasing length of the π stack and thus reflect experimental trends correctly. These results demonstrate that anion–(π)n–π interactions exist and matter, ready for use as a unique new tool in catalysis and beyond.
  • Dipole moment and polarizability of tunable Intramolecular charge transfer states in heterocyclic π‑conjugated molecular dyads determined by computational and Stark spectroscopic study
    E.J. Rohwer, M. Akbarimoosavi, S.E. Meckel, X. Liu, Y. Geng, L.M. Lawson Daku, A. Hauser, A. Cannizzo, S. Decurtins, R.J. Stanley, S.-X. Liu and T. Feurer
    Journal of Physical Chemistry C, 122 , 2018, p9346-9355
    DOI:10.1021/acs.jpcc.8b02268 | Abstract | Article HTML | Article PDF | Supporting Info
The annulation of two redox-active molecules into a compact and planar structure paves the way toward a new class of electronically versatile materials whose physical properties can be tuned via a substitution of one of the constituting moieties. Specifically, we present tetrathiafulvalene–benzothiadiazole donor–acceptor molecules. The critical role played by the dielectric properties of these molecules is evident by the large spectral shifts of the ground-state absorption spectra in a range of solvents. Stark spectroscopy is performed to determine experimentally dipole and polarizability change over transitions in the visible range with particular attention to the transition from the highest-occupied molecular orbital (HOMO) to the lowest-unoccupied molecular orbital (LUMO). The experimental results are compared to the results of time-dependent density functional theory calculations, and we reciprocally validate results from calculation and experiment. This allows us to filter out effective models and reveal important insights. The calculations are initially performed in the gas phase and subsequently a polarizable continuum model is adopted to probe the influence of the solvent on the molecular dielectric properties. The results show a large charge displacement from the HOMO to the LUMO and confirm the intramolecular charge transfer nature of the lowest-energy transition. Substitution of the acceptor moiety with electron-withdrawing groups results in changes to the experimentally determined molecular properties consistent with the effects predicted by computational results. The dominant contribution to the electroabsorption signal is due to the change in dipole moment, which is measured to be roughly 20 D for all samples and forms a small angle with the transition dipole moment in a toluene solvent environment.
A planarizable push–pull molecular probe with mechanosensitive properties was investigated at several biomimetic interfaces, consisting of different phospholipid monolayers located between dodecane and an aqueous buffer solution, using the interface-specific surface-second-harmonic-generation (SSHG) technique. Whereas the SSHG spectra recorded at liquid-disordered interfaces were similar to the absorption spectra in bulk solutions, those measured at liquid-ordered phases exhibited a remarkable shift towards lower energies to an extent depending on the surface pressure of the phospholipid monolayer. On the basis of quantum-chemical calculations, this effect was accounted for by the planarization of the mechanosensitive probe. Polarization-resolved SSHG measurements revealed that the average orientation of the probe at the interface is an even more sensitive reporter of lateral pressure and order than the spectral shape. Additionally, time-resolved SSHG measurements pointed to slower dynamics upon intercalation inside the phospholipid monolayer, most likely due to the more constrained environment. This study demonstrates that the concept of mechanosensitive optical probes can be further exploited when combined with a surface-selective nonlinear optical technique.
  • Membrane bound COMT isoform is an interfacial enzyme: general mechanism and new drug design paradigm
    A. Magarkar, P. Parkkila, T. Viitala, T. Lajunen, E. Mobarak, G. Licari, O. Cramariuc, E. Vauthey, T. Rg and A. Bunker
    Chemical Communications, 54 (28) , 2018, p3440-3443
    DOI:10.1039/C8CC00221E | Abstract | Article HTML | Article PDF
The enzyme catechol-O-methyltransferase (COMT) has water soluble (S-COMT) and membrane associated (MB-COMT), bitopic, isoforms. Of these MB-COMT is a drug target in relation to the treatment of Parkinson's disease. Using a combination of computational and experimental protocols, we have determined the substrate selection mechanism specific to MB-COMT. We show: (1) substrates with preferred affinity for MB-COMT over S-COMT orient in the membrane in a fashion conducive to catalysis from the membrane surface and (2) binding of COMT to its cofactor ADOMET induces conformational change that drives the catalytic surface of the protein to the membrane surface, where the substrates and Mg2+ ions, required for catalysis, are found. Bioinformatics analysis reveals evidence of this mechanism in other proteins, including several existing drug targets. The development of new COMT inhibitors with preferential affinity for MB-COMT over S-COMT is now possible and insight of broader relevance, into the function of bitopic enzymes, is provided.
  • On the mechanism of rapid metal exchange between thiolate-protected gold and gold/silver clusters: a time-resolved in situ XAFS study
    B. Zhang, O.V. Safonova, S. Pollitt, G. Salassa, A. Sels, R. Kazan, Y. Wang, G. Rupprechter, N. Barrabs and T. Brgi
    Physical Chemistry Chemical Physics, 20 (7) , 2018, p5312-5318
    DOI:10.1039/C7CP08272J | Abstract | Article HTML | Article PDF | Supporting Info
The fast metal exchange reaction between Au38 and AgxAu38−x nanoclusters in solution at −20 °C has been studied by in situ X-ray absorption spectroscopy (time resolved quick XAFS) in transmission mode. A cell was designed for this purpose consisting of a cooling system, remote injection and mixing devices. The capability of the set-up is demonstrated for second and minute time scale measurements of the metal exchange reaction upon mixing Au38/toluene and AgxAu38−x/toluene solutions at both Ag K-edge and Au L3-edge. It has been proposed that the exchange of gold and silver atoms between the clusters occurs via the SR(-M-SR)n (n = 1, 2; M = Au, Ag) staple units in the surface of the reacting clusters during their collision. However, at no point during the reaction (before, during, after) evidence is found for cationic silver atoms within the staples. This means that either the exchange occurs directly between the cores of the involved clusters or the residence time of the silver atoms in the staples is very short in a mechanism involving the metal exchange within the staples.
The applicability of room-temperature ionic liquids (RTILs) as inert solvents is generally based on their electrochemical window. We herein show that this concept has its limitations if RTILs are exposed to an oxidizing environment in the presence of light. Acetonitrile solutions of RTILs with 1-methyl-3-ethylimidazolium as cation and five different anions, including thiocyanate (SCN) and dicyanamide (DCA), were investigated. Upon addition of organic electron acceptors to solutions of RTILs with SCN or DCA, charge-transfer (CT) absorption bands due to the formation of donor–acceptor complexes between the anion and the electron acceptor were observed. Time-resolved measurements from the femtosecond to the microsecond regimes were used to investigate the nature and the excited-state dynamics of these complexes upon excitation in the CT band. We show that even though the RTILs are seemingly inert according to their electrochemical properties, the dicyanamide and thiocyanate based RTILs can actively participate in photochemical reactions in oxidizing environments and therefore differ from the behavior expected for an inert solvent. This has not only important implications for the long-term stability of RTIL-based systems but can also lead to misinterpretation of photochemical studies in these solvents.
  • Influence of the hydrogen-bond interactions on the excited-state dynamics of a push-pull azobenzene dye: the case of Methyl Orange
    C. Nanoz, G. Licari, J.S. Beckwith, M. Soederberg, B. Dereka, A. Rosspeintner, O. Yushchenko, R. Letrun, S. Richert, B. Lang and E. Vauthey
    Physical Chemistry Chemical Physics, 20 (10) , 2018, p7254-7264
    DOI:10.1039/C7CP08390D | Abstract | Article HTML | Article PDF | Supporting Info
The excited-state dynamics of the push–pull azobenzene Methyl Orange (MO) were investigated in several solvents and water/glycerol mixtures using a combination of ultrafast time-resolved fluorescence and transient absorption in both the UV-visible and the IR regions, as well as quantum chemical calculations. Optical excitation of MO in its trans form results in the population of the S2 ππ* state and is followed by internal conversion to the S1 nπ* state in ∼50 fs. The population of this state decays on the sub-picosecond timescale by both internal conversion to the trans ground state and isomerisation to the cis ground state. Finally, the cis form converts thermally to the trans form on a timescale ranging from less than 50 ms to several minutes. Significant differences depending on the hydrogen-bond donor strength of the solvents, quantified by the Kamlet Taft parameter α, were observed: compared to the other solvents, in highly protic solvents (α > 1), (i) the viscosity dependence of the S1 state lifetime is less pronounced, (ii) the S1 state lifetime is shorter by a factor of ≈1.5 for the same viscosity, (iii) the trans-to-cis photoisomerisation efficiency is smaller, and (iv) the thermal cis-to-trans isomerisation is faster by a factor of ≥103. These differences are explained in terms of hydrogen-bond interactions between the solvent and the azo nitrogen atoms of MO, which not only change the nature of the S1 state but also have an impact on the shape of ground- and excited-state potentials, and, thus, affect the deactivation pathways from the excited state.
The accurate description of transition metal complexes in liquid solutions is a challenging fundamental research problem, which must be tackled when it comes to understanding the role of the solvent in the photoinduced low-spin (LS) → high-spin (HS) transition in solvated Fe(II) complexes. We report an in-depth ab initio molecular dynamics (AIMD) study of the spin-state dependence of the structural and vibrational properties of the prototypical [Fe(bpy)3]2+ (bpy = 2,2'-bipyridine) LS complex in water. The description achieved for the LS and HS solution structures of aqueous [Fe(bpy)3]2+ significantly improves on and actually supersedes the one from our previous AIMD study [Lawson Daku and Hauser, J. Phys. Chem. Lett., 2010, 1, 1830], thanks to substantially longer simulation times and the use of the dispersion-corrected BLYP-D3 functional in place of the standard BLYP functional. The present results confirm the ≈0.19 Å lengthening of the Fe–N bonds and the increased thermal fluctuation of the molecular edifice stemming from the weakening of the Fe–N bonds upon the LS → HS change of states. Revisiting our previous finding on the solvation of  [Fe(bpy)3]2+, they indicate that the number of water molecules in its first hydration shell actually increases from ~15 in the LS state to ~17 in the HS state. The vibration modes and associated vibrational density of states (VDOS) of  [Fe(bpy)3]2+ have been determined from a generalized normal coordinate analysis. The VDOS of the Fe–N stretching and bending modes are located in the far-IR region. For LS [Fe(bpy)3]2+, the peak positions of the VDOS of the Fe–N stretching modes agree very well with the experimental Fe–N stretching frequencies. For HS  [Fe(bpy)3]2+, the spanned frequency range encompasses the Fe–N stretching frequency range reported for HS polypyridine Fe(II) complexes. The LS and HS IR spectra of the complex have also been calculated in the 0 ≤ ν ≤ 2500 cm-1 range from the dynamics of the Wannier function centers. The calculated LS IR spectrum matches available experimental data. The predicted HS–LS IR difference spectrum of aqueous [Fe(bpy)3]2+ shows mostly an increase in intensity upon the LS → HS change of states.
  • Correlating Boron-Hydrogen Stretching Frequencies with Boron-Hydrogen Bond Lengths in Closoboranes: An Approach Using DFT Calculations
    H. Hagemann, M. Sharma, D. Sethio and L.M. Lawson Daku
    Helvetica Chimica Acta, 101 (2) , 2018
    DOI:10.1002/hlca.201700239 | Abstract
  • Photocatalytic CO2 reduction by Cr-substituted Ba2(In2-xCrx )O5 ·(H2O)δ (0.04 ≤ x ≤ 0.60)
    S. Yoon, M. Gaul, S. Sharma, K. Son, H. Hagemann, D. Ziegenbalg, U. Schwingenschlogl, M. Widenmeyer and A. Weidenkaff
    Solid State Sciences, in press , 2018
    DOI:10.1016/j.solidstatesciences.2018.02.005 | Abstract
Cr-substituted polycrystalline Ba2(In2-xCrx)O5·(H2O)δ powders (0.04 ≤ x ≤ 0.60) were synthesized by solid state reaction to investigate the relation of crystal structure, thermochemical, magnetic, and optical properties. The Cr-substitution results in an unit cell expansion and formation of the higher-symmetric tetragonal phase together with increased oxygen and hydrogen contents. Magnetic property measurements reveal that the diamagnetic pristine Ba2In2O5·(H2O)δ becomes magnetically ordered upon Cr-substitution. By UV–vis spectroscopy a gradual shift of the absorption-edge energy to lower values was observed. Numerical calculations showed that the observed bandgap narrowing was ascribed to the Cr induced states near the Fermi level. The correlation between the changes of crystal chemistry, magnetic, and optical properties of Cr-substituted Ba2(In2-xCrx)O5·(H2O)δ can be explained by the replacement of In by Cr. Consequently, an enhanced photocatalytic CO2 reduction activity was observed with increasing Cr substitution, compatible with the state-of-the-art high surface area TiO2 photocatalyst (P-25).
  • Excimer-Based On-Off Bis(pyreneamide) Macrocyclic Chemosensors
    M. Vishe, T. Lathion, S. Pascal, O. Yushchenko, A. Homberg, E. Brun, E. Vauthey, C. Piguet and J. Lacour
    Helvetica Chimica Acta, 101 , 2018
    DOI:10.1002/hlca.201700265 | Abstract | Article HTML
A series of bis(pyreneamide) macrocycles, synthesized in two steps from THF, THP, oxepane and 1,4-dioxane, are tested as chemosensors for a large range of mono-, di- and trivalent cations. In their native states, these macrocycles exhibit a strong excimer fluorescence that is quenched upon the addition of the metal ions (alkaline, alkaline earth, p-, d-, and f-block metals). UV-Vis spectrophotometric titrations, cyclic voltammetry, excimer fluorescence quenching and transient absorption spectroscopy experiments helped characterize the On-Off changes occurring upon binding and demonstrate that the highest stability constants are obtained with divalent cations Ca2+ and Ba2+ specifically.
  • Energy Transfer and Charge Separation Dynamics in Photoexcited Pyrene-Bodipy Molecular Dyads
    M. Fakis, J. Beckwith, K. Seintis, E. Martinou, C. Nanoz, N. Karakostas, I.D Petsalakis, G. Pistolis and E. Vauthey
    Physical Chemistry Chemical Physics, 20 , 2018, p837-849
    DOI:10.1039/C7CP06914F | Abstract | Article PDF | Supporting Info
The photophysical properties of two pyrene-bodipy molecular dyads, composed of a phenyl-pyrene (Py-Ph) linked to the meso position of a bodipy (BD) molecule with either H-atoms (BD1) or ethyl groups (BD2) at the 2, 6 positions, are investigated by stationary, nanosecond and femtosecond spectroscopy. The properties of these dyads (Py-Ph-BD1 and Py-Ph-BD2) are compared to those of their constituent chromophores in two solvents namely 1,2 dichloroethane (DCE) and acetonitrile (ACN). Stationary spectroscopy reveals a weak coupling among the subunits in both dyads. Excitation of the Py subunit eads to emission that is totally governed by the BD subunits in both dyads pointing to excitation energy transfer (EET) from the Py to BD chromophore. Femtosecond fluorescence and transient absorption spectroscopy reveal that EET takes place within 0.3-0.5 ps and is mostly independent of the solvent and the type of the BD subunit. The EET lifetime is in reasonable agreement with that predicted by Förster theory. After EET has taken place, Py-Ph-BD1 in DCE and Py-Ph-BD2 in both solvents decay mainly radiatively to the ground state with 3.5 - 5.0 ns lifetimes which are similar to those of the individual BD chromophores. However, the excited state of Py-Ph-BD1 in ACN is quenched having a lifetime of 1 ns. This points to the opening of an additional non-radiative channel of the excited state of Py-Ph-BD1 in this solvent, most probably charge separation (CS). Target analysis of the TA spectra has shown that the CS follows an inverted kinetics and is substantially slower than the recombination of the charge-separated state. Occurrence of CS with Py-Ph-BD1 in ACN is also supported by energetic considerations. The above results indicate that only a small change in the structure of the BD units incorporated in the dyads, significantly affects the excited state dynamics leading either to a dyad with long lifetime and high fluorescence quantum yield or to a dyad with an intramolecular CS ability.
  • Photolabile Coumarins with Improved Efficiency through Azetidinyl Substitution
    G. Bassolino, C. Nanoz, Z. Thiel, E.M. Bois, E. Vauthey and P. Rivera-Fuentes
    Chemical Science, 9 , 2018, p387-391
    DOI:10.1039/C7SC03627B | Abstract | Article PDF | Supporting Info
Azetidinyl substituents have been recently used to improve the fluorescence quantum yield of several classes of fluorophores. Herein, we demonstrate that other useful photochemical processes can be modulated using this strategy. In particular, we prepared and measured the quantum yield of photorelease of a series of 7-azetidinyl-4-methyl coumarin esters and compared it to their 7-diethylamino and julolidine-fused analogues. The efficiency of the photorelease reactions of the azetidinyl-substituted compounds was 2- to 5-fold higher than the corresponding diethylamino coumarins. We investigated the origin of this effect in model fluorophores and in the photoactivatable esters, and found that H-bonding with the solvent seems to be the prominent deactivation channel inhibited upon substitution with an azetidinyl ring. We anticipate that this substitution strategy could be used to modulate other photochemical processes with applications in chemical biology, catalysis and materials science.
Investigating the photoinduced electronic and structural response of bistable molecular building blocks incorporating transition metals in solution phase constitutes a necessary stepping stone for steering their properties toward applications and performance optimizations. This work presents a detailed X-ray transient absorption (XTA) spectroscopy study of a prototypical spin crossover (SCO) complex [FeII(mbpy)3]2+ (where mbpy = 4,4′-dimethyl-2,2′-bipyridine) with an [FeIIN6] first coordination shell in water (H2O) and acetonitrile (CH3CN). The unprecedented data quality of the XTA spectra together with the direct fitting of the difference spectra in k space using a large number of scattering paths enables resolving the subtle difference in the photoexcited structures of an FeII complex in two solvents for the first time. Compared to the low spin (LS) 1A1 state, the average Fe–N bond elongations for the photoinduced high spin (HS) 5T2 state are found to be 0.181 ± 0.003 Å in H2O and 0.199 ± 0.003 Å in CH3CN. This difference in structural response is attributed to ligand–solvent interactions that are stronger in H2O than in CH3CN for the HS excited state. Our studies demonstrate that, although the metal center of [FeII(mbpy)3]2+ could have been expected to be rather shielded by the three bidentate ligands with quasi-octahedral coordination, the ligand field strength in the HS excited state is nevertheless indirectly affected by solvation effects that modifies the charge distribution within the Fe–N covalent bonds. More generally, this work highlights the importance of including solvation dynamics in order to develop a generalized understanding of the spin-state switching at the atomic level.
  • Characterization of di-4-ANEPPS with nano-black lipid membranes
    M. Tsemperouli and K. Sugihara
    Nanoscale, in press , 2017
    DOI:10.1039/C7NR05863B | Abstract | Article PDF | Supporting Info
We report a platform based on lateral nano-BLMs, where electrical measurements and fluorescence microscopy setup are combined, for the calibration of di-4-ANEPPS, a common voltage sensitive dye (VSD). The advantage of the setup is 1) its flexibility in the choice of lipids and the applied voltages, 2) its high stability that enables high voltage (500 mV) application and long time measurements, and 3) its fluorescence microscopy readout, which can be directly correlated with other fluorescence microscopy experiments using VSDs (e.g. membrane potential measurements in living cells). Using the setup, we observed that the calibration curve of di-4-ANEPPS highly depends on the net electric charge of the lipids. The developed setup can be used to calibrate VSDs in different lipid environment for understanding their fundamental voltage-sensing mechanism in future.
  • A stable 3 V all-solid-state sodium-ion battery based on a closo -borate electrolyte
    L. Duchne, R.-S. Khnel, E. Stilp, E.C. Reyes, A. Remhof, H. Hagemann and C. Battaglia
    Energy & Environmental Science, 10 (12) , 2017, p2609-2615
    DOI:10.1039/C7EE02420G | Abstract
The influence of the length of the push–pull branches of quadrupolar molecules on their excited-state symmetry breaking was investigated using ultrafast time-resolved IR spectroscopy. For this, the excited-state dynamics of an A-π-D-π-A molecule was compared with those of an ADA analogue, where the same electron donor (D) and acceptor (A) subunits are directly linked without a phenylethynyl π-spacer. The spatial distribution of the excitation was visualized in real time by monitoring C≡C and C≡N vibrational modes localized in the spacer and acceptor units, respectively. In nonpolar solvents, the excited state is quadrupolar and the excitation is localized on the π-D-π center. In medium polarity solvents, the excitation spreads over the entire molecule but is no longer symmetric. Finally, in the most polar solvents, the excitation localizes on a single D-π-A branch, contrary to the ADA analogue where symmetry breaking is only partial.
Most quadrupolar molecules designed for large two-photon absorption cross section have been shown to undergo symmetry breaking upon excitation to the S1 state. This was originally deduced from their strong fluorescence solvatochromism and later visualized in real time using transient infrared spectroscopy. For molecules not containing clear IR marker modes, however, a specific real-time observation of the symmetry breaking process remains lacking. Here we show that this process can be resolved using broadband fluorescence upconversion spectroscopy by monitoring the instantaneous emission transition dipole moment. This approach is illustrated with measurements performed on two quadrupolar molecules, with only one of them undergoing excited-state symmetry breaking in polar solvents.
The excited-state dynamics of an aniline–triazine electron donor–acceptor dyad with an alkyne spacer has been investigated using a combination of ultrafast broadband mid-IR and visible transient absorption and fluorescence spectroscopies. The transient IR data reveal the occurrence of an efficient alkyne to allene isomerization of the spacer with a time constant increasing from a few hundreds of femtoseconds to a few picoseconds with solvent viscosity. This process is faster than the vibrational cooling of the Franck–Condon excited state, indicative of nonequilibrium dynamics. The transient electronic absorption and fluorescence data evidence that this transformation is accompanied by a charge separation between the donor and the acceptor subunits. The allene character of the spacer implies an orthogonal orientation of the donor and acceptor moieties, similar to that proposed for twisted intramolecular charge-transfer states. Such states are often invoked in the excited-state dynamics of donor–acceptor dyads, but their involvement could never be unambiguously evidenced spectroscopically. The alkyne–allene isomerization involves not only a torsional motion but also a bending of the molecule due to the sp to sp2 rehybridization of one of the alkyne carbon atoms. This twisted and rehybridized intramolecular charge transfer (“TRICT”) state decays back to the planar and linear alkyne ground state on a time scale decreasing from a few hundred to ten picoseconds upon going from weakly to highly polar solvents. The different solvent dependencies reveal that the dynamics of the allene buildup are controlled by the structural changes, whereas the decay is limited by the charge recombination step.
Fluoride substitution in LiBH4 is studied by investigation of LiBH4-LiBF4 mixtures (9:1 and 3:1). Decomposition was followed by in-situ synchrotron radiation X-ray diffraction (in-situ SR-PXD), thermogravimetric analysis and differential scanning calorimetry with gas analysis (TGA/DSC-MS) and in-situ infrared spectroscopy (in-situ FTIR). Upon heating, fluoride substituted LiBH4 forms (LiBH4-xFx) and decomposition occurs, releasing diborane and solid decomposition products. The decomposition temperature is reduced more than fourfold relative to the individual constituents, with decomposition commencing at T / °C = 80 °C. The degree of fluoride substitution is quantified by sequential Rietveld refinement and shows a selective manner of substitution. In-situ FTIR experiments reveal formation of bands originating from LiBH4-xFx. Formation of LiF and observation of diborane release implies that the decomposing materials have a composition that facilitates formation of diborane and LiF, i.e. LiBH4-xFx (LiBH3F). An alternative approach for fluoride substitution was performed, by addition of Et3N∙3HF to LiBH4, yielding extremely unstable products. Spontaneous decomposition indicates fluoride substitution to have occurred. From our point of view, this is the most significant destabilization effect seen for borohydride materials so far.
The nucleation and growth properties of domains of molecules of the same state in open boundary three-dimensional (3D) spin-crossover systems of various shapes are discussed within the framework of the mechanoelastic model. The molecules are situated on face-centered-cubic lattices and are linked by springs through which they interact. Monte Carlo simulations imply that clusters nucleate from corners in the case of systems having well-developed faces and from kinks in the case of spherical samples, in accordance with available experimental data. In addition, a method to characterize the cooperativity in these systems is proposed, which by scanning the fluctuations in the 3D samples can be related directly to powder x-ray-diffraction experiments.
1,4-Dioxepines result from the decomposition of α-diazo-β-keto esters in the presence of oxetanes using the catalytic combination of the (cyclopentadienyl)ruthenium complex [CpRu(CH3CN)3][BArF] and 1,10-phenanthroline. The regioselective [4+3] insertions follow an SN1-like mechanism and occur yet enantiospecifically (es 74%). The retention of configuration was ascertained by vibrational circular dichroism (VCD) and solid state analyses. Furans, products of [4+1] insertions, are only observed as traces in the above protocol. To promote their formation under CpRu catalysis, it is necessary to use a two-step process with γ-halogenated alcohols as substrates.
The dynamics of unimolecular photo-triggered reactions can be strongly affected by the surrounding medium for which a large number of theoretical descriptions have been used in the past. An accurate description of these reactions requires knowing the potential energy surface and the friction felt by the reactants. Most of these theories start from the Langevin equation to derive the dynamics, but there are few examples comparing it with experiments. Here we explore the applicability of a Generalized Langevin Equation (GLE) with an arbitrary potential and a non-Markovian friction. To this end, we have performed broadband fluorescence measurements with sub-picosecond time resolution of a covalently linked organic electron donor-acceptor system in solvents of changing viscosity and dielectric permittivity. In order to establish the free energy surface (FES) of the reaction, we resort to stationary electronic spectroscopy. On the other hand, the dynamics of a non-reacting substance, Coumarin 153, provide the calibrating tool for the non-Markovian friction over the FES, which is assumed to be solute independent. A simpler and computationally faster approach uses the Generalized Smoluchowski Equation (GSE), which can be derived from the GLE for pure harmonic potentials. Both approaches reproduce the measurements in most of the solvents reasonably well. At long times, some differences arise from the errors inherited from the analysis of the stationary solvatochromism and at short times from the excess excitation energy. However, whenever the dynamics become slow, the GSE shows larger deviations than the GLE, the results of which always agree qualitatively with the measured dynamics, regardless of the solvent viscosity or dielectric properties. The method applied here can be used to predict the dynamics of any other reacting system, given the FES parameters and solvent dynamics are provided. Thus no fitting parameters enter the GLE simulations, within the applicability limits found for the model in this work.
Implementation, benchmarking, and representative applications of the new FDE-ADC(3) method for describing environmental effects on excited states as a combination of frozen density embedding (FDE) and the algebraic-diagrammatic construction scheme for the polarization propagator of third order (ADC(3)) are presented. Results of FDE-ADC(3) calculations are validated with respect to supersystem calculations on test systems with varying molecule–environment interaction strengths from dispersion up to multiple hydrogen bonds. The overall deviation compared to the supersystem calculations is as small as 0.029 eV for excitation energies, which is even smaller than the intrinsic error of ADC(3). The dependence of the accuracy on the choice of method and functional for the calculation of the environment and the nonelectrostatic part of the system–environment interaction is evaluated. In three representative examples, the FDE-ADC method is applied to investigate larger systems and to analyze excited state properties using visualization of embedded densities and orbitals.
The kinetic lability of hexadentate gallium-based tripods is sufficient to ensure thermodynamic self-assembly of luminescent heterodimetallic [GaLn(L3)3]6+ helicates on the hour time scale, where Ln is a trivalent 4f-block cation. The inertness is however large enough for preserving the triple-helical structure when [GaLn(L3)3]6+ is exposed to lanthanide exchange. The connection of a second gallium-based tripod further slows down the exchange processes to such an extent that spectroscopically active [CrErCr(L4)3]9+ can be diluted into closed-shell [GaYGa(L4)3]9+ matrices without metal scrambling. This feature is exploited for pushing molecular-based energy transfer upconversion (ETU) at room temperature.
A thorough understanding of the microscopic mechanism of excited-state proton transfer (ESPT) and the influence of the solvent environment on its dynamics are of great fundamental interest. We present here a detailed investigation of an ESPT to solvent (DMSO) using time-resolved broadband fluorescence and transient absorption spectroscopies. All excited-state species are resolved spectrally and kinetically using a global target analysis based on the two-step Eigen-Weller model. Reversibility of the initial short-range proton transfer producing excited contact ion pairs (CIP*) is observed unambiguously in fluorescence and must be explicitly considered to obtain the individual rate constants. Close inspection of the early dynamics suggests that the relative populations of the protonated form (ROH*) and CIP* are governed by solvent relaxation that influences the relative energies of the excited states. This constitutes a breakdown of the Eigen-Weller model, although the overall agreement between the data and the analysis using classical rate equations is excellent.
Cr-substituted and pristine Ba2In2O5·(H2O)x powders were synthesized by solid state reaction. The influence of Cr-substitution on the crystal structure, chemical composition, magnetic and optical properties were investigated. Powder X-ray diffraction (XRD), elemental analysis and TGA-MS reveal that with substitution of In for Cr, the unit cell volume and the unit cell parameter b increase together with the oxygen and hydrogen content. Magnetic property measurements indicate that Ba2In2O5·(H2O)x is diamagnetic in the temperature range of 2 K < T < 300 K becoming ferromagnetic upon Cr-substitution. In the UV–vis spectra of the Cr-substituted sample a distinctive shift of the absorption-edge energy from 430 to 690 nm was observed corresponding to a bandgap narrowing from 2.88 to 1.80 eV. The replacement of tetrahedral InO4 units by octahedral CrO6 units was found to be the main factor for the drastic change of the magnetic and optical properties.
Symmetry breaking of the excited state of a linear quadrupolar acceptor-donor-acceptor molecule was investigated using time-resolved infrared spectroscopy in 55 solvents allowing the influence of several solute–solvent interactions to be examined separately. No symmetry breaking was found in nonpolar solvents irrespective of their refractive index, indicating that differences in dispersion interactions between the two arms of the molecule do not suffice to induce an asymmetric distribution of the excitation. However, symmetry breaking was observed in nondipolar but quadrupolar solvents like benzene to an extent that can be as large as that found in medium dipolar solvents like THF. Whereas larger symmetry breaking occurs in the most dipolar solvents, the strongest are observed in protic solvents due to hydrogen bonding. Strong evidence of the formation of halogen bonds in the excited state is also presented, confirming the idea of symmetry-breaking-induced asymmetrical photochemistry.
Lithium amide–borohydrides Li[BH4]1–x[NH2]x possess liquid-like Li superionic conductivity at nearly ambient temperature. The fast Li+ diffusion facilitated by the localized motions of the anions is proposed to occur through a network of vacant tetrahedral sites, acting as conduction channels. To study the reorientational dynamics of the anions, we have performed quasielastic neutron scattering experiments on samples with different compositions (x = 2/3, 0.722, 0.737, 3/4) over a broad temperature and time range. To unambiguously disentangle the contributions of the two species, [BH4] and [NH2], we took advantage of deuterium labeling and could clearly demonstrate that the quasielastic broadening is mainly determined by the [BH4] reorientations. With the help of a newly developed model, supported by ab initio molecular dynamics calculations, we have identified three relaxation components, which account for generally anisotropic C3-rotations of the [BH4] tetrahedra including jumps by a small angle from the equilibrium position.
A strategy for late-stage electrophilic functionalizations of cationic helicenes is exposed. Thanks to strongly acidic conditions that permit reversible electrophilic substitutions, regioselective acylations, sulfonylations or alkylations occur at the extremity(ies) of the helical cores. Extended [5] or [6]helicenes can then be generated from cationic [4]helicenes in successive one-pot elongation processes. Retention of configuration and excellent enantiospecificity (up to 99%) are observed for the helicene growth in the enantiopure series.
  • Triplet state CPL active helicene-dithiolene platinum bipyridine complexes
    T. Biet, T. Cauchy, Q. Sun, J. Ding, A. Hauser, P. Oulevey, T. Brgi, D. Jacquemin, N. Vanthuyne, J. Crassous and N. Avarvari
    Chemical Communications, 53 (66) , 2017, p9210-9213
    DOI:10.1039/C7CC05198K | unige:96312 | Abstract | Article HTML | Article PDF | Supporting Info
Chiral metal dithiolene complexes represent a family of chiral precursors, which can give rise to molecular materials with properties resulting from the interplay of chirality with conductivity, magnetism, and photophysics. We describe herein the first examples of chiral metal diimine dithiolene complexes, by the use of a platinum(II) centre coordinated by 2,2’-bipyridine and helicene-dithiolene ligands. Straightforward synthesis of racemic and enantiopure complexes allows the preparation of luminescent Pt(bipy) [4] and [6]helicene compounds for which the solid-state structure was determined as well. TD-DFT calculations support the assignment of the low energy bands observed in the UV-vis absorption spectra as mixed metal-ligand-to-ligand charge transfer transitions and confirm that the emission band results from the T1 excited state. Interestingly the enantiopure [6]helicene complexes show CPL activity at room temperature in acetonitrile solutions with anisotropy factors of 3×10-4.
  • CrIII as an alternative to RuII in metallo-supramolecular chemistry
    D. Zare, B. Doistau, H. Nozary, C. Besnard, L. Gune, Y. Suffren, A.-L. Pel, A. Hauser and C. Piguet
    Dalton Transactions, 46 , 2017, p8992-9009
    DOI:10.1039/c7dt01747b | unige:95682 | Article HTML | Article PDF | Supporting Info
Compared with divalent ruthenium coordination complexes, which are widely exploited as parts of multi-component photonic devices, optically active trivalent chromium complexes are under-represented in multi-metallic supramolecular architectures performing energy conversion because of the tricky preparation of stable heteroleptic CrIII building blocks. We herein propose a kind of remedy with the synthesis of a novel family of kinetically inert hetereloptic bis-terdentate mononuclear complexes, which can be incorporated into dinuclear rod-like diads as a proof-of-concept. The mechanism and magnitude of intermetallic Cr···Cr communications have been unraveled by a combination of magnetic, photophysical and thermodynamic investigations. Alternated aromatic/alkyne connectors provided by Sonogashira coupling reactions emerge as the most efficient wires for long-distance communication between two chromium centres bridged by Janus-type back-to-back bis-terdentate receptors.
  • A Lithium Amide-Borohydride Solid-State Electrolyte with Lithium-Ion Conductivities Comparable to Liquid Electrolytes
    Y. Yan, R.-S. Khnel, A. Remhof, L. Duchne, E.C. Reyes, D. Rentsch, Z. Lodziana and C. Battaglia
    Advanced Energy Materials, 2017, p1700294
    DOI:10.1002/aenm.201700294 | Abstract | Article HTML | Article PDF | Supporting Info
High ionic conductivity of up to 6.4 ×10−3S cm−1 near room temperature  (40 °C) in lithium amide-borohydrides is reported, comparable to values  of liquid organic electrolytes commonly employed in lithium-ion batteries.  Density functional theory is applied coupled with X-ray diffraction, calorimetry, and nuclear magnetic resonance experiments to shed light on the  conduction mechanism. A Li4Ti5O12 half-cell battery incorporating the lithium amide-borohydride electrolyte exhibits good rate performance up to 3.5 mA cm−2 (5 C) and stable cycling over 400 cycles at 1 C at 40 °C, indicating high bulk and interfacial stability. The results demonstrate the potential of lithium amide-borohydrides as solid-state electrolytes for high-power lithium-ion batteries.
The fluorescence quenching of organic dyes via H-bonding interactions is a well-known phenomenon. However, the mechanism of this Hydrogen-Bond Induced Nonradiative Deactivation (HBIND) is not understood. Insight into this process is obtained by probing in the infrared the O H stretching vibration of the solvent after electronic excitation of a dye with H-bond accepting cyano groups. The fluorescence lifetime of this dye was previously found to decrease from 1.5 ns to 110 ps when going from an aprotic solvent to the strongly protic hexafluoroisopropanol (HFP). Prompt strengthening of the H-bond with the dye was identified by the presence of a broad positive O-H band of HFP, located at lower frequency than the O-H band of the pure solvent. Further strengthening occurs within a few picoseconds before the excited H-bonded complex decays to the ground state in 110 ps. The latter process is accompanied by the dissipation of energy from the dye to the solvent and the rise of a characteristic hot solvent band in the transient spectrum. Polarization-resolved measurements evidence a collinear alignment of the nitrile and hydroxyl groups in the H-bonded complex, which persists during the whole excited-state lifetime. Measurements in other fluorinated alcohols and in chloroform/HFP mixtures reveal that the HBIND efficiency depends not only on the strength of the H-bond interactions between the dye and the solvent but also on the ability of the solvent to form an extended H-bond network. The HBIND process can be viewed as an enhanced internal conversion of an excited complex consisting of the dye molecule connected to a large H-bond network.
K3Fe(CN)6 reacts with the viologen 1,1′-bis(2,4-dinitrophenyl)-4,4′-bipyridinium dication, (DNP)2+, to form a supramolecular complex, (DNP)3[Fe(CN)6]2·10H2O (1). The crystal structure of 1 reveals that there are two [Fe(CN)6]3– anions within an organic framework of three (DNP)2+ cations with the shortest Fe(III)···Fe(III) distances of ca. 9.8 Å, distances that minimize extensive long-range magnetic exchange coupling interactions between the [Fe(CN)6]3– anions, and, thus, 1 is paramagnetic above ca. 17 K and exhibits weak ferromagnetic coupling between 17 and 3 K and antiferromagnetic coupling between 3 and 1.8 K. The long Fe(III)···Fe(III) distances permit slow spin–spin and slow spin–lattice paramagnetic relaxation, relative to the iron-57 Larmor precession frequency, as is evidenced by the Mössbauer spectra measured between 3 and 60 K; between 85 and 295 K, rapid paramagnetic relaxation is observed. Both the slow spin–spin and slow spin–lattice relaxation are mediated by the organic, π-conjugated viologen cations. The Fe–C distances, the Mössbauer isomer shifts, the temperature dependence of the magnetic susceptibility, and the 3 K magnetization results all indicate the presence of low-spin Fe(III) ions in the [Fe(CN)6]3– anions in 1. There is no unequivocal indication of the presence of any formal electron delocalization or transfer from the [Fe(CN)6]3– anion to the (DNP)2+ cations in the results obtained from X-ray crystallography, magnetic measurements, and Mössbauer spectra. Because of enhancement of the spin–orbit coupling by the heavy-atom or -ion effect, the Fe(III) ions in the [Fe(CN)6]3– anions interact with the (DNP)2+ cations, causing them to fluoresce with increasing intensity upon cooling from 90 to 25 K when excited at 300 nm. The resulting luminescence of the viologen (DNP)2+ cation induced by the [Fe(CN)6]3– anions indicates the presence of significant mixing of the molecular orbitals derived from the [Fe(CN)6]3– anions and the molecular orbitals associated with the (DNP)2+ cations to yield bonding supramolecular orbitals in 1, a mixing that is also observed between 50 and 3 K in the temperature dependence of the isomer shift of 1.
A CuAu38 bimetallic nanocluster was synthesized by adding a single copper atom to the Au38(2-PET)24 nanocluster. The absence of CuxAu38(2-PET)24 doped species was demonstrated by MALDI-TOF mass spectrometry. A separation of bimetallic clusters was attained for the first time where isomers of the E2 enantiomer of the Au38Cu1(2-PET)24 adduct were successfully isolated from their parent cluster using chiral HPLC. The CD of the isolated isomers revealed a change in their electronic structure upon copper addition. The luminescence of the Au38Cu1 adduct is significantly enhanced in comparison with the parent Au38 nanocluster. The stability of the newly formed adduct is strongly dependent on the coexistence of the Au38 nanoclusters.
Enhancement of infrared signals from polyelectrolyte adsorbed on gold nanoparticles (GNPs) was studied in situ by attenuated total reflection infrared spectroscopy. Nanoparticles and polyelectrolytes were deposited using layer-by-layer techniques, and the infrared signal was studied as a function of particle size, particle density, and distance from particle surface. It was observed that enhancement is more pronounced for larger nanoparticles and it decreases with increasing distance from the particle surface. Furthermore, at high GNP coverage, the signal from the first polyelectrolyte layer is particularly enhanced, and the signal increases slowly with time, in contrast to subsequent layers. We assign this to polyelectrolyte adsorption within narrow gaps between nanoparticles, where the electric field is enhanced. Furthermore, enhanced absorption was observed in the gap between the GNPs and the germanium internal reflection element, which was confirmed by polarized measurements. This enhancement is more pronounced for silver particles, and it represents a promising route for analysis of surfaces by infrared spectroscopy.
The ligand exchange reaction between heteroatom doped (Pd, Pt) Au25(2-PET)18 (2-PET = 2-phenylethylthiolate) clusters and enantiopure 1,1′-binaphthyl-2,2′-dithiol (BINAS) was monitored in situ using chiral high-performance liquid chromatography (HPLC). During the ligand exchange reactions, replacement of two protecting thiols (2-PET) with one new entering BINAS ligand on the cluster surface occurs. The rigid dithiol BINAS adsorbs in a specific mode that bridges the apex and one core site of two adjacent S(R)–Au–S(R)–Au–S(R) units. This is the most favorable binding mode and theoretically preserves the original structure. A kinetic investigation on these in situ ligand exchange reactions revealed a decrease in reactivity after multiple exchange. A comparison of relative rate constants demonstrates a similar exchange rate toward BINAS for both (Pd, Pt) systems. The possible structural deformation after incorporation of BINAS was investigated by X-ray absorption spectroscopy (XAS) at the S K-edge and Au L3-edge. First, a thorough assignment of all sulfur contributions to the XANES spectrum was performed, distinguishing for the first time long and short staple motifs. Following that, a structural comparison of doped systems using XANES and EXAFS confirmed the unaltered Au25 structure, except for some slight influence on the Au–S bonds. Additionally, an intact staple motif was confirmed after incorporation of rigid dithiol BINAS by both XANES and EXAFS. This finding agrees with a BINAS interstaple binding mode predicted by calculation, which does not perturb the cluster structure.
We report the DFT study of the vibrational spectroscopy properties of Mg(B3H8)2, a potential intermediate in the decomposition of Mg(BH4)2, as well as those of CB11H12 and CB9H10, whose salts can exhibit high ionic conductivities. Because the inclusion of anharmonicity is key to the accurate description of the vibrational properties of BH species [D. Sethio, L. M. Lawson Daku, H. Hagemann. Int. J. Hydrogen Energy, 41 (2016) 6814], the calculations were performed both in the harmonic and in the anharmonic approximation. The IR and Raman spectra of Cs(CB11H12) and Na2(B10H10) have also been measured. The calculated and experimental spectra are in good agreement. A comparative analysis of the vibrational spectroscopy properties is made for B3H8 and Mg(B3H8)2, B12H122− and CB11H12, and for B10H102− and CB9H10.
  • Artificial tubular connections between cells based on synthetic lipid nanotubesOpen access paper
    A. Kozintsev and K. Sugihara
    RSC Advances, 7 (33) , 2017, p20700-20708
    DOI:10.1039/C7RA02187A | unige:94060 | Abstract | Article HTML | Article PDF
Tunneling nanotubes (TNTs) have become a major topic of interest as a form of intercellular communication due to their recent discovery. However, research on this subject has often suffered from a lack of controllability in the generation of the nanotubular connections. In this work, we demonstrate a simplified approach to selectively create a direct nanotubular connection between eukaryotic cells by manually manipulating self-assembling lipid nanotubes (LNTs) from inverted hexagonal-phase lipid blocks. The technique requires minimal instrumentation for creating the LNT connection between cells compared to conventional approaches. Based on the diffusion of fluorescent lipids from LNTs into cell membranes (D = 0.032 ± 0.003 μm2 s−1), the probability of observing membrane fusion between LNTs and cell membranes was estimated as 30%. Among these cell–LNT junctions the resulting structure is open-ended roughly 75% of the time, as evidenced from observations of the diffusion of a water-soluble dye between two cells connected with this nanotubular structure.
We propose a simple method for predicting the spin state of homoleptic complexes of the Fe(II) d6 ion with chelating diimine ligands. The approach is based on the analysis of a single metric parameter within a free (noncoordinated) ligand: the interatomic separation between the N-donor metal-binding sites. An extensive analysis of existing complexes allows the determination of critical N···N distances that dictate the regions of stability for the high-spin and low-spin complexes, as well as the intermediate range in which the magnetic bistability (spin crossover) can be observed. The prediction has been tested on several complexes that demonstrate the validity of our method.
A simple model has been developed to describe the symmetry-breaking of the electronic distribution of AL–D–AR type molecules in the excited state, where D is an electron donor and AL and AR are identical acceptors. The origin of this process is usually associated with the interaction between the molecule and the solvent polarization that stabilizes an asymmetric and dipolar state, with a larger charge transfer on one side than on the other. An additional symmetry-breaking mechanism involving the direct Coulomb interaction of the charges on the acceptors is proposed. At the same time, the electronic coupling between the two degenerate states, which correspond to the transferred charge being localised either on AL or AR, favours a quadrupolar excited state with equal amount of charge-transfer on both sides. Because of these counteracting effects, symmetry breaking is only feasible when the electronic coupling remains below a threshold value, which depends on the solvation energy and the Coulomb repulsion energy between the charges located on AL and AR. This model allows reproducing the solvent polarity dependence of the symmetry-breaking reported recently using time-resolved infrared spectroscopy.
The first catalytic kinetic resolution by N-sulfonylation is described. 2-Substituted indolines are resolved (s=2.6–19) using an atropisomeric 4-dimethylaminopyridine-N-oxide (4-DMAP-N-oxide) organocatalyst. Use of 2-isopropyl-4-nitrophenylsulfonyl chloride is critical to the stereodiscrimination and enables facile deprotection of the sulfonamide products with thioglycolic acid. A qualitative model that accounts for the stereodiscrimination is proposed.
The adsorption of a DNA fluorescent probe belonging to the thiazole orange family at the dodecane/water and dodecane/phospholipid/water interfaces has been investigated using a combination of surface second harmonic generation (SSHG) and all-atomistic molecular dynamics (MD) simulations. Both approaches point to a high affinity of the cationic dye for the dodecane/water interface with a Gibbs free energy of adsorption on the order of −45 kJ/mol. Similar affinity was observed with a monolayer of negatively charged DPPG (1,2-dipalmitoyl-sn-glycero-3-phospho-rac-(1-glycerol)) lipids. On the other hand, no significant adsorption could be found with the zwitterionic DPPC (1,2-dipalmitoyl-sn-glycero-3-phosphocholine) lipids. This was rationalized in terms of Coulombic interactions between the monolayer surface and the cationic dye. The similar affinity for the interface with and without DPPG, despite the favorable Coulombic attraction in the latter case, could be explained after investigating the interfacial orientation of the dye. In the absence of a monolayer, the dye adsorbs with its molecular plane almost flat at the interface, whereas in the presence of DPPG it has to intercalate into the monolayer and adopt a significantly different orientation to benefit from the electrostatic stabilization.
  • A highly stable sodium solid-state electrolyte based on a dodeca/deca-borate equimolar mixture
    L. Duchne, R.-S. Khnel, D. Rentsch, A. Remhof, H. Hagemann and C. Battaglia
    ChemComm, 53 (30) , 2017, p4195-4198
    DOI:10.1039/C7CC00794A | unige:93532 | Abstract | Article HTML | Article PDF
Na2(B12H12)0.5(B10H10)0.5, a new solid-state sodium electrolyte is shown to offer high Na+ conductivity of 0.9 mS cm-1 at 20 °C, excellent thermal stability up to 300 °C, and a large electrochemical stability window of 3 V including stability towards sodium metal anodes, all essential prerequisites for a stable room-temperature 3 V all-solid-state sodium-ion battery.
Polar solvation dynamics of six 7-aminocoumarins and 4-aminophthalimide (4AP) are investi- gated using broadband FLuorescence UP–conversion Spectroscopy (FLUPS) combined with a global analysis based on time-dependent band-shape functions. The solvation dynamics of the coumarins in ethanol exhibit only minor differences but are, however, significantly different from that of 4AP. The band-shape parameters, width and asymmetry, exhibit much larger variation even among the coumarins and are correlated with the amount of excess excitation energy. Differences in the solvation dynamics of 4AP and a selected coumarin, C151, are also observed in dimethyl sulfoxide demonstrating the molecularity of solvation i.e. solvation depends on the solute and does not solely reflect the dynamic properties of the solvent. These differences are attributed to specific solute-solvent interactions due to hydrogen bonding. In a weakly interacting solvent, benzonitrile, the solvation dynamics of 4AP and C151 are nearly identical.
Alkaline or alkaline earth octahydrotriborate M(B3H8)x and dodecahydro-closo-dodecaborate MxB12H12 (M = Li, Na, Mg or Ca with x = 1 or 2) have recently attracted a lot of interest for hydrogen storage and solid electrolyte applications. Nevertheless, their syntheses are still a roadblock for large scale applications. In this paper we propose a novel approach for their syntheses starting from the cheapest borohydride NaBH4. The process involves first the solvothermal synthesis of tetrabutylammonium octahydrotriborate (C4H9)4NB3H8 (TBAB3H8) being the basis for the syntheses of the others boranes. Starting from TBAB3H8, we have synthesized pure and unsolvated NaB3H8 by salt metathesis reaction with sodium tetraphenylborate. Then, we have successfully obtained Na2B12H12 by solvothermal decomposition of NaB3H8. This approach has shown to be quantitative and reproducible, which could lead to the development of these boranes in real life applications.
Because of its crucial role in many areas of science and technology, photoinduced electron transfer is the most investigated photochemical reaction. Despite this, several important questions remain open. We present recent efforts to answer some of them, which concern both inter- and intramolecular processes. The decisive factor that allowed these issues to be successfully addressed was the use of time-resolved infrared (TRIR) spectroscopy.

Many different transient species, such as tight and loose ion pairs (TIPs and LIPs) and exciplexes, have been invoked to explain the dynamics of intermolecular photoinduced charge separation reactions (i.e., electron transfer between two neutral species) and the production of free ions. However, their structures are essentially unknown, and their exact roles in the reaction mechanism are unclear. Indeed, the commonly used transient electronic absorption spectroscopy does not give much structural insight and cannot clearly distinguish ion pairs from free ions, at least in the visible region. Unambiguous spectral signatures of TIPs, LIPs, and exciplexes could be observed in the IR using electron donor/acceptor (D/A) pairs with adequate vibrational marker modes. The ability to spectrally distinguish these intermediates allowed their dynamics to be disentangled and their roles to be determined. Structural information could be obtained using polarization-resolved TRIR spectroscopy. Our investigations reveal that moderately to highly exergonic reactions result in the formation of both TIPs and LIPs. TIPs are not only generated upon direct charge-transfer excitation of DA complexes, as usually assumed, but are also formed upon static quenching with reactant pairs at distances and orientations enabling charge separation without diffusion. On the other hand, dynamic quenching produces primarily LIPs. In the case of highly exergonic reactions, strong indirect evidence for the generation of ion pairs in an electronic excited state was found, accounting for the absence of an inverted region. Finally, weakly exergonic reactions produce predominantly exciplexes, which can evolve further into ion pairs or recombine to the neutral ground state.

The high sensitivity of specific vibrational modes to the local electronic density was exploited to visualize the photoinduced charge flow in symmetric A–(π–D)2- and D–(π–A)2-type molecules developed for their two-photon absorption properties. The electronic ground state and Franck–Condon S1 state of these molecules are purely quadrupolar, but the strong solvatochromism of their fluorescence points to a highly dipolar relaxed S1 state. This has been explained in terms of excited-state symmetry breaking induced by solvent and/or structural fluctuations. However, real-time observation of this process was missing. Direct visualization of symmetry-breaking charge transfer was achieved using TRIR spectroscopy by monitoring vibrations localized in the two arms of these molecules. A transition from a purely quadrupolar state to a symmetry-broken state on the timescale of solvent relaxation could be clearly observed in polar solvents, indicating that symmetry breaking occurs primarily via solvent fluctuations. In the case of the D–(π–A)2 molecule, this breaking results in different basicities at the two A ends and consequently in different affinities for H-bonds, which in turn leads to the formation of an asymmetric tight H-bonded complex in highly protic solvents.

  • Mechanosensitivity of polydiacetylene with a phosphocholine headgroup
    R.D. Ortuso, U. Cataldi and K. Sugihara
    Soft Matter, 13 (8) , 2017, p1728-1736
    DOI:10.1039/C6SM02579J | unige:92341
We demonstrated colorimetric and fluorescence detection of peptide, melittin, with polydiacetylene (PDA) made of 1,2-bis(10,12-tricosadiynoyl)-sn-glycero-3-phosphocholine (DC(8,9)PC). The PDA used in this work has a phosphocholine headgroup, which mimics peptide-cell membrane interactions better than the conventional PDA assays with carboxyl headgroup. The dose curve (colorimetric response vs melittin concentration) showed a half maximum response at the melittin concentration of 0.1 mg/ml, which is similar to the traditional PDA assays. It suggests that the replacement of the headgroup was achieved without sacrificing the sensitivity. From the dose curve, Hill coefficient was extracted as αHill = 2.1. The value is in agreement with previous melittin studies with standard phospholipids, which reflects the benefit of having a biologically relevant headgroup. In addition, we found an unexpectedly slow spectral change when DC(8,9)PC-PDA was incubated with melittin. The origin of the time-dependent signal was studied by combining UV/VIS spectroscopy, fluorescence spectroscopy and dynamic light scattering.
A model for simulating the transient electronic absorption spectra of donor–acceptor dyads undergoing ultrafast intramolecular charge transfer in solution has been developed. It is based on the stochastic multichannel point-transition approach and includes the reorganization of high-frequency intramolecular modes (treated quantum mechanically) and of low frequency intramolecular and solvent modes (described classically). The relaxation of the slow modes is assumed to be exponential with time constants taken from experiments. The excited-state dynamics is obtained by simulating the population distribution of each quantum state after optical excitation and upon electronic and vibrational transitions. This model was used to simulate the transient electronic absorption spectra measured previously with a pyrylium phenolate in acetonitrile. A very good agreement between the simulated and measured spectra was obtained assuming a three-level model including the ground state, the optically excited state, and a dark state with large charge-transfer character and a substantially different geometry relative to that of the optically excited state. The merit of this approach to disentangle the contributions of both population changes and relaxation processes to the ultrafast spectral dynamics will be discussed.
  • Original oxo-centered bismuth oxo-arsenates; Critical effect of PO4 for AsO4 substitution
    J. Olchowka, M. Colmont, A. Aliev, T. Tran, P. Shiv Halasyamani, H. Hagemann and O. Mentr
    CrystEngComm, 19 , 2017, p936-945
    DOI:10.1039/C6CE02466A | unige:92340 | Abstract | Article HTML | Article PDF | Supporting Info
This work deals with the synthesis and crystal structure study of new bismuth oxo-arsenates and their oxo-phosphates homologous: Bi6ZnO7(AsO4)2 vs Bi6ZnO7(PO4)2 and Bi3.667Cd3O4(AsO4)3 vs Bi3Cd4O4(PO4)3. Their crystal structures were solved using single crystal X-Ray Diffraction. These are two other examples of crystal structures built on ribbon-like polycations formed of the linkage of oxo-centered O(Bi,M)4 tetrahedra sharing edges and surrounded by isolated XO4 groups (X= As or P), where the O(Bi,M)4 units are derived from the fluorite topology structure. Dealing with Bi6ZnO7(PO4), its acentric space group was confirmed by preliminary second harmonic generation (SHG). The P/As substitution led to a centrosymmetric space group due to local reorientation of oxo-anions. This is strongly related to steric effects between AsO4 (d As-O= 1.6-1.7Å) and PO4 (d P-O= 1.4-1.5Å). Concerning Bi3.667Cd3O4(AsO4)3 and Bi3Cd4O4(PO4)3, they show a second example of the reorientation of the XO4 groups depending of the X chemical nature. Finally, we present an original topology of oxo-centered units obtained with Bi5KO5(AsO4). The photoluminescence properties of Bi5KO5(AsO4) and Bi6ZnO7(AsO4)2 were also investigated. The first one emits at room temperature in the reddish-orange range (single band peak at 615nm assigned to the Bi3+: 3P11S0 transition whereas the second exhibits a weak emission in the green range (peak at 530nm). Its intriguing temperature dependence is discussed in the paper.
Ultrafast photochemical reactions in liquids occur on similar or shorter time scales compared to the equilibration of the optically populated excited state. This equilibration involves the relaxation of intramolecular and/or solvent modes. As a consequence, the reaction dynamics are no longer exponential, cannot be quantified by rate constants, and may depend on the excitation wavelength contrary to slower photochemical processes occurring from equilibrated excited states. Such ultrafast photoinduced reactions do no longer obey the Kasha–Vavilov rule. Nonequilibrium effects are also observed in diffusion-controlled intermolecular processes directly after photoexcitation, and their proper description gives access to the intrinsic reaction dynamics that are normally hidden by diffusion. Here we discuss these topics in relation to ultrafast organic photochemical reactions in homogeneous liquids. Discussed reactions include intra- and intermolecular electron- and proton-transfer processes, as well as photochromic reactions occurring with and without bond breaking or bond formation, namely ring-opening reactions and cis–trans isomerizations, respectively.
The possibility of the direct encapsulation of living cells via two-photon induced photopolymerization enables the microfabrication of hydrogel scaffolds with high initial cell loadings and intimate matrix-cell contact. While highly efficient water-soluble two-photon initiators based on benzylidene ketone dyes have been developed, they exhibit considerable cyto- and phototoxicity. To address the problem of photoinitiator migration from the extracellular matrix into the cytosol, a two-photon initiator bound to a polymeric hyaluronan backbone (HAPI) was synthesized in this work. HAPI exhibited a distinct improvement of cytocompatibility compared to a reference two-photon initiator. Basic photophysical investigations were performed to characterize the absorption and fluorescence behavior of HAPI. Laser scanning microscopy was used to visualize and confirm the hindered transmembrane migration behavior of HAPI. The performance of HAPI was tested in two-photon polymerization at exceedingly high printing speeds of 100 mm s-1 producing gelatin-based complex 3D hydrogel scaffolds with a water content of 85%. The photodamage of the structuring process was low and viable MC3T3 cells embedded in the gel were monitored for several days after structuring.
Introduction of heterocycles in the helical skeleton of helicenes allows modulation of their redox, chiroptical and photophysical properties. Herein, we describe the straightforward preparation and structural characterization by single crystal X-ray diffraction of thiadiazole-[7]helicene, which has been resolved into (M) and (P) enantiomers by chiral HPLC, together with its S-shaped double [4]helicene isomer, as well as the smaller congeners thiadiazole-[5]helicene and benzothiadiazole-anthracene. A copper(II) complex with two thiadiazole-[5]helicene ligands has been structurally characterized and it shows the presence of both (M) and (P) isomers coordinated to the metal centre. The emission properties of the unprecedented heterohelicenes are highly dependent on the helical turn, as the [7]- and [5]helicene are poorly emissive, whereas their isomers, that is, the S-shaped double [4]helicene and thiadiazole-benzanthracene, are luminescent, with quantum efficiencies of 5.4% and 6.5%, respectively. DFT calculations suggest a quenching of the luminescence of enantiopure [7]helicenes through an intersystem crossing mechanism arising from the relaxed excited S1 state.
Ultrafast time-resolved infrared spectroscopy of [Ru(bpy)3]2+ (bpy = 2,2’-bipyridine), [Ru(mbpy)3]2+ (mbpy = 6-methyl-2,2’-bipyridine), and [Ru(mphen)3]2+ (mphen = 2-methyl-1,10’-phenanthroline) in deuterated acetonitrile serves to elucidate the evolution of the system following pulsed excitation into the 1MLCT band at 400 nm. Whereas for [Ru(bpy)3]2+ no intermediate state can be evidenced for the relaxation of the corresponding 3MLCT state back to the ground state, for [Ru(mbpy)3]2+ and [Ru(mphen)3]2+ an intermediate state with a lifetime of about 400 ps is observed. The species associated IR difference spectra of this state are in good agreement with the calculated difference spectra of the lowest energy 3dd state using DFT. The calculated potential energy curves for all the complexes in the triplet manifold along the metal-ligand distance show that for [Ru(bpy)3]2+ the 3dd state is at higher energy than the 3MLCT state and that there is a substantial barrier between the two minima. For [Ru(mbpy)3]2+ and [Ru(mphen)3]2+, the 3dd state is at lower energy than the 3MLCT state.
Sum frequency mixing of fluorescence and ∼1300 nm gate pulses, in a thin β-barium borate crystal and non-collinear type II geometry, is quantified as part of a femtosecond fluorimeter [X.-X. Zhang et al., Rev. Sci. Instrum. 82, 063108 (2011)]. For a series of fixed phasematching angles, the upconversion efficiency is measured depending on fluorescence wavelength. Two useful orientations of the crystal are related by rotation around the surface normal. Orientation A has higher efficiency (factor ∼3) compared to B at the cost of some loss of spectral coverage for a given crystal angle. It should be used when subtle changes of an otherwise stationary emission band are to be monitored. With orientation B, the fluorescence range λF > 420-750 nm is covered with a single setting of the crystal and less gate scatter around time zero. The accuracy of determining an instantaneous emission band shape is demonstrated by comparing results from two laboratories.
We present experimental Raman optical activity (ROA) spectra of enantio-enriched single-walled carbon nanotubes (SWCNTs). Enantiomeric samples of (6,5) SWCNTs were prepared using nonlinear density gradient ultracentrifugation (DGU). Upon excitation at 2.33 eV, remarkably strong G-band signals are obtained due to strong resonance enhancement with the E22S transition of (6,5) SWCNTs. Enhancement allows measuring the vibrational optical activity (VOA) at unusually low concentrations. The obtained results are in good agreement with the single-excited-state theory (SES). To our knowledge, these are the first experimental VOA spectra of SWCNTs.
Multiple Ag atoms were doped inside Au38(SCH2CH2Ph)24 nanoclusters using the metal exchange method for the first time for the synthesis of AgxAu38–x(SCH2CH2Ph)24. MALDI-TOF mass spectrometry revealed the time dependence of the synthesis. Cluster species with different numbers of Ag atoms (different x values) migrate differently on a chromatography (HPLC) column, which allows one to isolate cluster samples with a narrowed distribution of exchanged metal atoms. The enantiomers of selected AgxAu38–x(SCH2CH2Ph)24 samples (average x = 6.5 and 7.9) have been separated by HPLC. Doping changes the electronic structure, as is evidenced by the significantly different CD spectra. UV–vis spectra of the doped sample also show diminished features. The temperature required for complete racemization follows Au38 > AgxAu38–x (x = 6.5) > AgxAu38–x (x = 7.9). To our surprise, the racemization of AgxAu38–x(SCH2CH2Ph)24 (x = 7.9) occurred even at 20 °C. Racemization involves a rearrangement of the staple motifs at the cluster surface. The results therefore show an increased flexibility of the cluster with increasing silver content. The weaker Ag–S bonds compared to Au–S are proposed to be at the origin of this observation. The experimentally determined activation energy for the racemization is ca. 21.5 kcal/mol (x = 6.5) and 19.5 kcal/mol (x = 7.9), compared to 29.5 kcal/mol for Au38(SCH2CH2Ph)24, suggesting no complete metal–S bond breaking in the process.
We describe for the first time the crystallization in thin films of a DNA copolymer composed of a low molecular weight chitosan backbone to which a sequence of nucleic acids is grafted (chitosan-g-ssDNA). As assessed by atomic force microscopy, optical microscopy and spectroscopy, crystallization occurs due to intermolecular hydrogen bonding in which the nucleic acid strands engage. The morphology of the crystals depends on the affinity for the surface of the polymer segments that compose the DNA copolymer hybrid. The nucleic acids adsorb on mica and silica on which side-branched structures are observed whereas chitosan interacts preferentially with gold, and dendritic crystals are assembled. Attenuated total reflectance infrared spectroscopy supports the high ordering of the structure and the establishment of strong intermolecular interactions by hydrogen bonding.
  • Control of the plasmonic resonance of a graphene coated plasmonic nanoparticle array combined with a nematic liquid crystalOpen access paper
    L. De Sio, U. Cataldi, T. Brgi, N. Tabiryan and T.J. Bunning
    AIP Advances, 6 (7) , 2016, p75114
    DOI:10.1063/1.4959869 | unige:94066 | Abstract | Article HTML | Article PDF
We report on the fabrication and characterization of a switchable plasmonic device based on a conductive graphene oxide (cGO) coated plasmonic nanoparticle (NP) array, layered with nematic liquid crystal (NLC) as an active medium. A monolayer of NPs has been immobilized on a glass substrate through electrostatic interaction, and then grown in place using nanochemistry. This monolayer is then coated with a thin (less then 100nm) cGO film which acts simultaneously as both an electro-conductive and active medium. The combination of the conductive NP array with a separate top cover substrate having both cGO and a standard LC alignment layer is used for aligning a NLC film in a hybrid configuration. The system is analysed in terms of morphological and electro-optical properties. The spectral response of the sample characterized after each element is added (air, cGO, NLC) reveals a red-shift of the localized plasmonic resonance (LPR) frequency of approximately 62nm with respect to the NP array surrounded by air. The application of an external voltage (8Vpp) is suitable to modulate (blue shift) the LPR frequency by approximately 22nm.
The catalytic photo-oxidation of 3,4-dihydroxybenzoic acid on TiO2 has been studied by in situ ATR-FTIR in flowing water and in flowing wet air/nitrogen gas. In flowing water it was difficult to observe photodegradation intermediates despite photocatalytic action during UV illumination. In the flowing wet air/nitrogen system carboxylic acids and carbonates were observed. It was shown that water plays an important role in the formation of oxidation active species. Oxygen shows a prominent role for carboxylic acid degradation, but the photogenerated hole plays the important role for the 3,4-dihydroxybenzoic acid ring cleavage.
We have studied, both experimentally and theoretically, the Raman vibrational spectra of a series of n-alkanethiolate protected Au25(SCnH2n+1)18 clusters, with n = 2, 3, 4, 5, 6, 8, 10, 12, and 14. The C–H stretching region of the infrared spectra reveals that, while shorter chains are flexible, longer chains are more ordered with a propensity toward extended all-trans conformation. The different behavior of long and short chains is also reflected in the low-frequency Raman spectra of the clusters, which are broadened for the longer chains due to interchain interactions and formation of bundles. The experimental low-frequency modes in the Raman spectra, associated with Au–S stretching vibrations, change drastically and in an apparently unsystematic way as a function of chain length. For example, a band around 320 cm–1 associated with tangential Au–S stretching character shifts up in frequency, then down and then up again as the carbon chain is increased. DFT calculations reveal that this behavior is due to a nonlinear coupling of this mode to torsional and bending modes of the alkyl chain. The frequencies of these modes strongly depend on the chain length and, as a consequence, also their coupling with the Au–S stretching modes, which explains the erratic behavior of this band in the spectra. This behavior is well described by calculations on a mimic cluster model that considers only one staple motif. For the ethanethiolate-protected cluster, the entire cluster was included in the calculation of the Raman spectrum, and this allowed for the first time to compare directly experimental and calculated Raman spectra of the same cluster. Furthermore, our study shows that the entire ligand has to be considered for the calculation of the low frequency vibrations of the Au–S interface, as this spectral region is sensitive to coupling with low-frequency ligand modes.
  • Optical control of plasmonic heating effects using reversible photo-alignment of nematic liquid crystals
    G. Palermo, U. Cataldi, L. De Sio, T. Brgi, N. Tabiryan and C. Umeton
    Applied Physics Letters, 109 , 2016, p191906
    DOI:10.1063/1.4967377 | unige:94069 | Abstract | Article HTML | Article PDF
We demonstrate and characterize an optical control of the plasmonic heat delivered by a monolayer substrate of gold nanoparticles, obtained by modulating the effective refractive index of the neighboring dielectric medium. The effect, which exploits the dependence of the nematic liquid crystal (NLC) refractive index on the molecular director orientation, is realized by using a polarization dependent, light-induced molecular reorientation of a thin film of photo-alignment layer that the NLC is in contact with. For a suitable alignment, plasmonic pumping intensity values ranging from 0.25 W/cm2 to 6.30 W/cm2 can induce up to 17.4 °C temperature variations in time intervals of the order of seconds. The reversibility of the optically induced NLC molecular director orientation enables an active control of the plasmonic photo-induced heat.
  • Self-assembled Lipid Structures as Model Systems for Studying Electrical and Mechanical Properties of Cell Membranes
    K. Sugihara
    Chimia, 70 (11) , 2016, p805-809
    DOI:10.2533/chimia.2016.805 | unige:90820 | Abstract
This mini review summarizes our recent works in the development of electrical and mechanical characterization tools for cell membranes. These research topics require the application of physical and chemical characterization tools to biological systems, thus are very interdisciplinary.
  • Room Temperature Magnetic Switchability Assisted by Hysteretic Valence Tautomerism in a Layered Two Dimensional Manganese-Radical Coordination Framework
    A. Lannes, Y. Suffren, J.B. Tommasino, R. Chiriac, F. Toche, L. Khrouz, F. Molton, C. Duboc, I. Kieffer, J.-L. Hazemann, C. Reber, A. Hauser and D. Luneau
    Journal of the American Chemical Society, 138 (50) , 2016, p16493-16501
    DOI:10.1021/jacs.6b10544 | unige:90821 | Abstract | Article HTML | Article PDF | Supporting Info
The manganese-nitronyl-nitroxide two dimensional coordination polymer {[Mn2(NITIm)3]ClO4}n (1) (NITImH = 2-(2-imidazolyl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-3-oxide-1-oxyl) undergoes an unusual hysteretic thermoinduced valence tautomeric transition near room temperature, during which the manganese(II) ions are oxidized to manganese(III) and two of the three deprotonated radicals (NITIm-) are reduced to their diamagnetic aminoxyl form (denoted NITImRed2-). Upon cooling, the high-temperature species {[MnII2(NITIm)3]ClO4}n (1HT) turns into the low-temperature species {[MnIII2(NITImRed)2(NITIm)]ClO4}n (1LT) around 274 K, while on heating the process is reversed at about 287 K. This valence tautomeric phenomenon is supported by temperature-dependent magnetic susceptibility measurements, differential scanning calorimetry (DSC), crystal structure determination, UV-vis absorption, X-ray absorption (XAS) an emission (XES) and Electron Paramagnetic Resonance (EPR) spectroscopies in the solid-state.
  • Physicochemical and Electronic Properties of Cationic [6]Helicenes: from Chemical and Electrochemical Stabilities to Far-Red (Polarized) Luminescence
    J. Bosson, G.M. Labrador, S. Pascal, F.-A. Miannay, O. Yushchenko, H. Li, L. Bouffier, N. Sojic, R.C. Tovar, G. Muller, D. Jacquemin, A.D. Laurent, B. Le Guennic, E. Vauthey and J. Lacour
    Chemistry - A European Journal, 22 (51) , 2016, p18394-18403
    DOI:10.1002/chem.201603591 | unige:90268 | Abstract | Article HTML | Article PDF | Supporting Info
The physicochemical properties of cationic dioxa (1), azaoxa (2), and diaza (3) [6]helicenes demonstrate a much higher chemical stability of the diaza adduct 3 (pKR+=20.4, Ered1/2 =−0.72 V) compared to its azaoxa 2 (pKR+=15.2, Ered1/2=−0.45 V) and dioxa 1 (pKR+=8.8, Ered1/2=−0.12 V) analogues. The fluorescence of these cationic chromophores is established, and ranges from the orange to the far-red regions. From 1 to 3, a bathochromic shift of the lowest energy transitions (up to 614 nm in acetonitrile) and an enhancement of the fluorescence quantum yields and lifetimes (up to 31 % and 9.8 ns, respectively, at 658 nm) are observed. The triplet quantum yields and circularly polarized luminescence are also reported. Finally, fine tuning of the optical properties of the diaza [6]helicene core is achieved through selective and orthogonal post-functionalization reactions (12 examples, compounds 415). The electronic absorption is modulated from the orange to the far-red spectral range (560–731 nm), and fluorescence is observed from 591 to 755 nm with enhanced quantum efficiency up to 70 % (619 nm). The influence of the peripheral auxochrome substituents is rationalized by first-principles calculations.
Symmetry-breaking charge transfer upon photoexcitation of a linear A-π-D-π-A molecule (D and A being electron donating and accepting groups) could be visualized using ultrafast time-resolved infrared spectroscopy by monitoring the CN stretching modes on the A units. Whereas in apolar solvents, the S1 state remains symmetric and quadrupolar, symmetry breaking occurs within ca. 100 fs in polar solvents as shown by the presence of two CN bands, instead of one in apolar solvents, with a splitting that increases with polarity. In protic solvents, symmetry breaking is significantly amplified by H-bonding interactions, which are the strongest at the CN group with the highest basicity. In strongly protic solvents, the two CN bands transform in about 20 ps into new bands with a larger splitting, and the lifetime of the S1 state is substantially reduced. This is attributed to the formation of an excited asymmetric tight H-bond complex.
Terpyridine derivatives are of great interest due to their unique photophysical properties when used as antennas in metallic complexes. Several experimental and theoretical studies indicate strong charge-transfer character of the lowest electronic excited state, which could be exploited for predicting fluorescence quantum yields from the magnitude of the charge separation induced by electronic transitions. Focusing on substituted 4′-phenyl-2,2′:6′2′′-terpyridyl, we report on two measures of the charge separation obtained from high-level calculations in ground and excited states (length of the change of the dipole moment and the electron–hole distance). Our refined model confirms that the fluorescence quantum yield shows a global S-shape dependence on the magnitude of the charge separation, which can be quantified either by the change in dipole moments between the ground and excited states or by the associated charge–hole distances. This approach provides a remarkable tool for the molecular design of a fluorescent polyaromatic antenna.
Germanium – polyelectrolyte – gold nanoparticle composites were prepared and characterized using FTIR-ATR spectroscopy and scanning electron microscopy. The germanium (Ge) element served as internal reflection element and the buildup of the layered system was followed in situ. Positively charged polyelectrolyte poly (allylamine hydrochloride) (PAH) adsorbs spontaneously on negatively charged Ge. Citrate-stabilized gold nanoparticles can then be adsorbed onto the PAH layer. Upon illumination of the device with visible light a prominent absorption over the entire mid infrared region is observed which is due to intervalence band transitions in Ge. The strong infrared signals are evidence for holes in the valence band of the Ge semiconductor, which arise due to electron transfer to the gold nanoparticles (GNP). The electron transfer, as evidenced by the holes in Ge, is affected by the nature of the gap between the Ge and the GNP. Increasing the gap by adsorbing polyelectrolyte multilayers hinders the electron transfer. Also heating and vacuum have a pronounced effect. The device is proposed as a sensor, where the sensing event is transduced into an optical signal in the infrared, as demonstrated for a thiol molecule. The thiol has a large affinity for the gold and therefore affects the germanium – gold nanoparticle gap. This reduces the electron transfer and therefore the absorption in the infrared upon illumination with visible light. Removal of the thiol from the solution leads to a recovering of the signal.
  • Configurationally Stable Doubly Bridged Biphenyl Azocines through Copper-Catalyzed Double Carbene Insertions into the Corresponding Azepines
    S. Harthong, E. Brun, S. Grass, C. Besnard, T. Brgi and J. Lacour
    Synthesis, 48 (19) , 2016, p3254-3262
    DOI:10.1055/s-0035-1562467 | unige:86678 | Abstract | Article HTML | Article PDF | Supporting Info
Doubly bridged biphenyl azocines can be prepared in a single step through copper-catalyzed reactions of a doubly bridged biphenyl azepine and diazodiester reagents. Double [1,2]-Stevens rearrangements occur at 100 °C to afford doubly tethered eight-membered rings (49 to 61%) as trans and cis regioisomers (1:1 ratio). These products present an axial chirality. ECD and VCD analyses of the separated enantiomers (CSP-HPLC) were used to assign the absolute configuration. High configurational stability is observed for both regioisomers as racemization does not occur after 1 week of heating at 208 °C in dodecane (ΔG > 41 kcal·mol–1). Interestingly, reactions performed at 40 °C retain a certain level of enantiospecificity (82–86%), avoiding, for the most part, thermal racemization of the starting material.
Ionic liquids (ILs) are receiving increasing interest for their use in synthetic laboratories and industry. Being composed of charged entities, they show a complex and widely unexplored dynamic behavior. Chiral ionic liquids (CILs) have a high potential as solvents for use in asymmetric synthesis. Chiroptical methods, owing to their sensitivity towards molecular conformation, offer unique possibilities to study the structure of these chiral ionic liquids. Raman optical activity proved particularly useful to study ionic liquids composed of amino acids and the achiral 1-ethyl-3-methylimidazolium counterion. We could substantiate, supported by selected theoretical methods, that the achiral counterion adopts an overall chiral conformation in the presence of chiral amino acid ions. These findings suggest that in the design of chiral ionic liquids for asymmetric synthesis, the structure of the achiral counter ion also has to be carefully considered.
  • Gold Nanowire Fabrication with Surface-Attached Lipid Nanotube Templates
    K. Jajcevic, M. Chami and K. Sugihara
    Small, 12 (35) , 2016, p4830-4836
    DOI:10.1002/smll.201600431 | unige:87903 | Abstract | Article HTML | Article PDF

A high-throughput approach to fabricate gold nanowires on surfaces with a lipid nanotube template is demonstrated. Streptavidin-coated gold nanoparticles are attached to the biotin-tagged lipid nanotubes. After the chemical fixation, the samples are dried and treated with oxygen plasma to remove the organic template and connect the particles. The created nanowires are characterized by cryo-transmission electron microscopy, atomic force microscopy, and electrical measurements.
A fast redistribution of metal atoms occurs upon mixing the AgxAu38−x and Au38 nanoclusters in solution, as observed by mass spectrometry. Physical separation of AgxAu38−x and Au38 species by a dialysis membrane prohibits the metal migration, which suggests that collisions between the reacting clusters are at the origin of the observation.
Here we reproduce the static and dynamical properties of spin-crossover complexes in the framework of the mechanoelastic model applied to triangular lattices. The switching processes between the high-spin and low-spin states are studied by combining the Monte Carlo method with the elastic lattice relaxation. The transition probabilities between the two states take into account intrinsic parameters, the values of which are approximated from experimental quantities (e.g., the energy gap, and the degeneracy ratio from the thermodynamic enthalpy and the entropy difference between the states), and the elastic force or elastic energy stored in the springs connecting the spin-changing centres. The value of the corresponding spring constant is estimated from the experimentally determined variation of the ligand-field strengths in the two spin states due to the cooperativity and the bulk modulus. Both simulated hysteresis loops and relaxation curves are in agreement with experimental data. Cooperativity related phenomena such as like-spin domain formation and the evolution of the interaction distribution with the HS fraction are also analysed.
Borohydrides have attained high interest in the past few years due to their high volumetric and gravimetric hydrogen content. Synthesis of di/trimetallic borohydride is a way to alter the thermodynamics of hydrogen release from borohydrides. Previously reported preparations of M(BH4)2 involved chloride containing species such as SrCl2. The presence of residual chloride (or other halide) ions in borohydrides may change their thermodynamic behavior and their decomposition pathway. Pure monometallic borohydrides are needed to study decomposition products without interference from halide impurities. They can also be used as precursors for synthesizing di/trimetallic borohydrides. In this paper we present a way to synthesize halide free alkaline earth metal (Sr, Ba) and europium borohydrides starting with the respective hydrides as precursors. Two novel high temperature polymorphs of Sr and Eu borohydrides and four polymorphs of Ba borohydride have been characterized by synchrotron X-ray powder diffraction, thermal analysis, and Raman and infrared spectroscopy and supported by periodic DFT calculations. The decomposition routes of these borohydrides have also been investigated. In the case of the decomposition of strontium and europium borohydrides, the metal borohydride hydride (M(BH4)H3, M = Sr, Eu) is observed and characterized. Periodic DFT calculations performed on room temperature Ba(BH4)2 revealed the presence of bidentate and tridentate borohydrides.
Organic molecules imprinting can be used for introducing specific properties and functionalities such as chirality to mesoporous materials. Particularly organic self-assemblies can work as a scaffold for templating inorganic materials such as silica. During recent years chiral imprinting of anionic surfactant for fabrication of twisted rod-like silica structures assisted by co-structuring directing agent were thoroughly investigated. The organic self-assemblies of anionic surfactants can also be used for introducing other shapes in rod-like silica structures. Here we report the formation of amphiphilic N-miristoyl-L-alanine self-assemblies in aqueous solution upon stirring and at presence of L-arginine. These anionic surfactant self-assemblies form fibers that grow by increasing the stirring duration. The fibers were studied using transmission electron microscopy, infra-red spectroscopy and vibrational circular dichroism. Addition of silica precursor 1,2-bis(triethoxysilyl)ethylene and co-structuring directing agent N-trimethoxysilylpropyl-N,N,N-trimethylammonium chloride at different stages of fibers’ growth leads to formation of different silica structures. By controlling stirring duration, we obtained twisted tubular silica structures as a result of fibers encapsulation. We decorated these structures with gold nanoparticles by different methods and measured their optical activity.
  • Cooperative Enhancement versus Additivity of Two-Photon-Absorption Cross Sections in Linear and Branched Squaraine Superchromophores
    H. Ceymann, A. Rosspeintner, M.H. Schreck, C. Mtzel, A. Stoy, E. Vauthey and C. Lambert
    Phys. Chem. Chem. Phys., 18 (24) , 2016, p16404-16413
    DOI:10.1039/C6CP02312F | unige:85610 | Abstract | Article HTML | Article PDF | Supporting Info
The linear and nonlinear optical properties of a series of oligomeric squaraine dyes were investigated by one-photon absorption spectroscopy (1PA) and two-photon absorption (2PA) induced fluorescence spectroscopy. The superchromophores are based on two indolenine squaraine dyes with transoid (SQA) and cisoid configuration (SQB). Using these monomers, linear dimers and trimers as well as star-shaped trimers and hexamers with benzene or triphenylamine cores were synthesised and investigated. The red-shifted and intensified 1PA spectra of all superchromophores could well be explained by exciton coupling theory. In the linear chromophore arrangements we also found superradiance of fluorescence but not in the branched systems. Furthermore, the 2PA showed enhanced cross sections for the linear oligomers but only additivity for the branched systems. This emphasizes that the enhancement of the 2PA cross section in the linear arrangements is probably caused by orbital interactions of higher excited configurations.
  • First time combination of frozen density embedding theory with the algebraic diagrammatic construction scheme for the polarization propagator of second order
    S. Prager, A. Zech, F. Aquilante, A. Dreuw and T.A. Wesolowski
    The Journal of Chemical Physics, 144 (20) , 2016, p204103
    DOI:10.1063/1.4948741 | unige:84472 | Abstract | Article HTML | Article PDF
The combination of Frozen Density Embedding Theory (FDET) and the Algebraic Diagrammatic Construction (ADC) scheme for the polarization propagator for describing environmental effects on electronically excited states is presented. Two different ways of interfacing and expressing the so-called embedding operator are introduced. The resulting excited states are compared with supermolecular calculations of the total system at the ADC(2) level of theory. Molecular test systems were chosen to investigate molecule–environment interactions of varying strength from dispersion interaction up to multiple hydrogen bonds. The overall difference between the supermolecular and the FDE-ADC calculations in excitation energies is lower than 0.09 eV (max) and 0.032 eV in average, which is well below the intrinsic error of the ADC(2) method itself.
Exposure of PdAu24(2-PET)18 (2-PET: 2-phenylethylthiolate) to BINAS (1,1-binaphthyl-2,2-dithiol) leads to species of composition PdAu24(2-PET)18−2x(BINAS)x due to ligand exchange reactions. The BINAS adsorbs in a specific mode that bridges the apex and one core site of two adjacent S(R)–Au–S(R)–Au–S(R) units. Species with different compositions of the ligand shell can be separated by HPLC. Furthermore, site isomers can be separated. For the cluster with exactly one BINAS in its ligand shell only one isomer is expected due to the symmetry of the cluster, which is confirmed by High-Performance Liquid Chromatography (HPLC). Addition of a second BINAS to the ligand shell leads to several isomers. In total six distinguishable isomers are possible for PdAu24(2-PET)14(BINAS)2 including two pairs of enantiomers concerning the adsorption pattern. At least four distinctive isomers are separated by HPLC. Calculations indicate that one of the six possibilities is energetically disfavoured. Interestingly, diastereomers, which have an enantiomeric relationship concerning the adsorption pattern of chiral BINAS, have significantly different stabilities. The relative intensity of the observed peaks in the HPLC does not reflect the statistical weight of the different isomers. This shows, as supported by the calculations, that the first adsorbed BINAS molecule influences the adsorption of the second incoming BINAS ligand. In addition, experiments with the corresponding Pt doped gold cluster reveal qualitatively the same behaviour, however with slightly different relative abundances of the corresponding isomers. This finding points towards the influence of electronic effects on the isomer distribution. Even for clusters containing more than two BINAS ligands a limited number of isomers were found, which is in contrast to the corresponding situation for monothiols, where the number of possible isomers is much larger.
Considered at the beginning of the 21th century as being incompatible with the presence of closely bound high-energy oscillators, lanthanide-centered superexcitation, which is the raising of an already excited electron to an even higher level by excited-state energy absorption, is therefore a very active topic strictly limited to the statistical doping of low-phonon bulk solids and nanoparticles. We show here that molecular lanthanide-containing coordination complexes may be judiciously tuned to overcome these limitations and to induce near-infrared (NIR)-to-visible (VIS)-light upconversion via the successive absorption of two low-energy photons using linear-optical responses. Whereas single-ion-centered excited-state absorption mechanisms remain difficult to implement in lanthanide complexes, the skillful design of intramolecular intermetallic energy-transfer processes operating in multimetallic architectures is at the origin of the recent programming of erbium-centered molecular upconversion.
The cooperativity index in a metallopolymer can be thought of as an estimation of the level of available water in nature. In a river, the water molecules can only feed immediate surroundings. Those in an aqueduct possess sufficient potential energy to extend this beneficial effect to wider areas. Twenty centuries ago, the Romans exploited this concept for extending their settlement in Western Europe. A reliable access to allosteric cooperativity indexes might push host–guest chemistry toward unexplored areas. More information can be found in the Full Paper by C. Piguet et al. (DOI: 10.1002/chem.201600857).


The basic concept of allosteric cooperativity used in biology, chemistry and physics states that any change in the intermolecular host–guest interactions operating in multisite receptors can be assigned to intersite interactions. Using lanthanide metals as guests and linear multi-tridentate linear oligomers of variable lengths and geometries as hosts, this work shows that the quantitative modeling of metal loadings requires the consideration of a novel phenomenon originating from solvation processes. It stepwise modulates the intrinsic affinity of each isolated site in multisite receptors, and this without resorting to allosteric cooperativity. An easy-to-handle additive model predicts a negative power law dependence of the intrinsic affinity on the length of the linear metallopolymer. Applied to lanthanidopolymers, the latter common analysis overestimates cooperativity factors by more than two orders of magnitude.

  • Functionalized Cationic [4]Helicenes with Unique Tuning of Absorption, Fluorescence and Chiroptical Properties up to the Far-Red Range Open access paper
    I.H. Delgado, S. Pascal, A. Wallabregue, R. Duwald, C. Besnard, L. Gune, C. Nanoz, E. Vauthey, R. Tovar, J. Lunkley, G. Muller and J. Lacour
    Chemical Science, 7 (7) , 2016, p4685-4693
    DOI:10.1039/C6SC00614K | unige:84734 | Abstract | Article HTML | Article PDF | Supporting Info
Unprecendented regioselective post-functionalization of racemic and enantiopure cationic diaza [4]helicenes is afforded. The peripheral auxochrome substituents allow a general tuning of the electrochemical, photophysical and chiroptical properties of the helical dyes (26 examples). For instance, electronic absorption and circular dichroism are modulated from the orange to near-infrared spectral range (575-750 nm), fluorescence quantum efficiency is enhanced up to 0.55 (631 nm) and circularly polarized luminescence is recorded in the red (│glum│ ~ 10-3)
Two reactive hydride composite systems, Ca(BH4)2–NaNH2 and Mg(BH4)2–NaNH2, were systematically studied by in situ synchrotron radiation powder diffraction, in situ Fourier transform infrared spectroscopy, thermogravimetric analysis and differential scanning calorimetry coupled with mass spectrometry. Metathesis reactions between the amides and borohydrides take place in both systems between 100°C and 150°C yielding amorphous materials with the proposed composition M(BH4)(NH2). Simultaneously, a fraction of NaNH2 decomposes to Na3N and ammonia via a complex pathway. The main gas released under 300°C is ammonia for both systems, while significant amounts of hydrogen are released only above 350°C.
The characterization of boron-hydrogen compounds is an active research area which encompasses subjects as diverse as the chemistry and structures of closoboranes or the thermal decomposition mechanism of the borohydrides. Due to their high gravimetric hydrogen content, borohydrides are considered as potential hydrogen storage materials. Their thermal decompositions are multistep processes, for which the intermediate products are not easily identified. To help address this issue, we have extensively investigated the vibrational and NMR properties of 21 relevant Bm boron-hydrogen species (m = 1–12; n = 1–14; z = 0–2) within density functional theory. We could thus show that the B3LYP-D2 dispersion-corrected hybrid can be used in combination with the large cc-pVTZ basis set for the reliable prediction of the 11B and 1H NMR spectra of the boron-hydrogen species, and also for the reliable prediction of their IR and Raman spectra while taking into account the anharmonicity of their molecular vibrations.
Polydiacetylene (PDA) is a conductive polymer that has a mechanochromism. When the polymer is exposed to mechanical stresses, change in temperature (thermochromism), pH (ionochromism) etc., the structural perturbation can be seen by the change in its color. Although it presents interesting electrical and optical properties, the relationship between these signals has rarely been investigated. We studied the correlation between the electrical conductivity and the absorption spectra of PDA. Upon UV irradiation, PDA absorption spectra presented a blue shift, which coincided with the decrease in the electrical conductivity.
Most symmetric quadrupolar molecules designed for two-photon absorption behave as dipolar molecules in the S1 electronic excited state. This is usually explained by a breakup of the symmetry in the excited state. However, the origin of this process and its dynamics are still not fully understood. Here, excited-state symmetry breaking in a quadrupolar molecule with a D-π-A-π-D motif, where D and A are electron donating and accepting units, is observed in real time using ultrafast transient infrared absorption spectroscopy. The nature of the relaxed S1 state was found to strongly depend on the solvent polarity: (1) in nonpolar solvents, it is symmetric and quadrupolar; (2) in weakly polar media, the quadrupolar state observed directly after excitation transforms to a symmetry broken S1 state with one arm bearing more excitation than the other; and (3) in highly polar solvents, the excited state evolves further to a purely dipolar S1 state with the excitation localized entirely on one arm. The time scales associated with the transitions between these states coincide with those of solvation dynamics, indicating that symmetry breaking is governed by solvent fluctuations.
  • Spectroscopy and chemical bonding in transition metal complexes
    A. Hauser and C. Reber
    in "Structure and Bonding" Springer, 172 , 2016, p291-312
    DOI:10.1007/430_2015_195 | unige:89169 | Abstract | Article PDF
Optical spectroscopy of transition metal complexes plays an important role in establishing excited state electronic and nuclear structures and thus in the elucidation of the multitude of photophysical and photochemical relaxation processes. The most important advances in this area of research over the past decade are due to the development of new experimental techniques such as ultrafast spectroscopy as well as structure determination in conjunction with other methods such as high pressure and variable temperature techniques. In this contribution, several paradigmatic systems, namely of complexes if chromium(III), iron(II), ruthenium(II), nickel(II), platinum(II) and palladium(II), are discussed with regard to their excited electronic and nuclear structures and photophysical relaxation processes.
  • Frozen-density embedding theory with average solvent charge densities from explicit atomistic simulations
    A. Laktionov, E. Chemineau-Chalaye and T.A. Wesolowski
    Phys. Chem. Chem. Phys., 18 (31) , 2016, p21069-21078
    DOI:10.1039/C6CP00497K | unige:86906 | Abstract | Article HTML | Article PDF
Besides molecular electron densities obtained within the Born–Oppenheimer approximation (ρB(r)) to represent the environment, the ensemble averaged density (〈ρB〉(r)) is also admissible in frozen-density embedding theory (FDET) [Wesolowski, Phys. Rev. A, 2008, 77, 12054]. This makes it possible to introduce an approximation in the evaluation of the solvent effect on quantum mechanical observables consisting of replacing the ensemble averaged observable by the observable evaluated at ensemble averaged ρB(r). This approximation is shown to affect negligibly the solvatochromic shift in the absorption of hydrated acetone. The proposed model provides a continuum type of representation of the solvent, which reflects nevertheless its local structure, and it is to be applied as a post-simulation analysis tool in atomistic level simulations
A molecular pentad comprised of a central multielectron donor and two flanking photosensitizer-acceptor moieties was prepared in order to explore the possibility of accumulating two positive charges at the central donor, using visible light as an energy input. Photoinduced charge accumulation in purely molecular systems without sacrificial reagents is challenging, because of the multitude of energy-wasting reaction pathways that are accessible after excitation with two photons. As expected, the main photoproduct in our pentad is a simple electron–hole pair, and it is tricky to identify the desired two-electron oxidation product on top of the stronger signal resulting from one-electron oxidation.
The properties of binary mixtures of dimethylsulfoxide and glycerol, measured by several techniques, are reported. Special attention is given to those properties contributing or affecting chemical reactions. In this respect the investigated mixture behaves as a relatively simple solvent and it is especially well suited for studies on the influence of viscosity in chemical reactivity. This is due to the relative invariance of the dielectric properties of the mixture. However, special caution must be taken with specific solvation, as the hydrogen-bonding properties of the solvent changes with the molar fraction of glycerol.
SrAl2O4 doped with europium and dysprosium is a powerful and widely used afterglow material. Within this material strontium is found in two crystallographic different sites. Due to the similar ion radii and same charge, Eu2+-ions can occupy both sites, resulting in two different Eu2+-ions, one emitting in the blue and one in the green spectral range. The blue emission is thermally quenched at room temperature. In this paper we investigate the energy transfer between different Eu ions depending on the concentration and temperature using two different approaches: lifetime measurements and integrated intensity. We find an activation energy for the thermal quenching of the blue emission of 0.195 ± 0.023 eV and a critical radius for the energy transfer of 3.0 ± 0.5 nm. This results can help in designing better afterglow materials due to the fact that with energy transfer parts of the lost emission in the blue region at room temperature can be converted to the green site.
Late endosomes are a major trafficking hub in the cell at the crossroads between endocytosis, autophagy, and degradation in lysosomes. Herein is disclosed the first small molecule allowing their selective imaging and monitoring in the form of a diazaoxatriangulene fluorophore, 1a (hexadecyl side chain). The compound is prepared in three steps from a simple carbenium precursor. In nanospheres, this pH-sensitive (pKa = 7.3), photochemically stable dye fluoresces in the red part of visible light (601 and 578 nm, acid and basic forms, respectively) with a quantum yield between 14 and 16% and an excited-state lifetime of 7.7–7.8 ns. Importantly, the protonated form 1a·H+ provokes a specific staining of late endosome compartments (pH 5.0–5.5) after 5 h of incubation with HeLa cells. Not surprisingly, this late endosome marking depends on the intra-organelle pH, and changing the nature of the lipophilic chain provokes a loss of selectivity. Interestingly, fixation of the fluorophore is readily achieved with paraformaldehyde, giving the possibility to image both live and fixed cells.
The properties of a series of oxazole yellow dyes, including the dicationic YOPRO-1 and its homodimeric parent YOYO-1 and two monocationic dyes (YOSAC-1 and YOSAC-3), have been investigated at the dodecane/water interface using stationary and time-resolved surface second harmonic generation (SSHG) combined with quantum chemical calculations. Whereas YOYO-1 exists predominantly as a H-dimer in aqueous solution, the stationary SSHG spectra reveal that such dimers are not formed at the interface. No significant H-aggregation was observed with YOPRO-1, neither in solution nor at the interface. In the case of the monocationic YOSAC dyes, a distinct SSHG band due to H-aggregates was measured at the interface, whereas only weak aggregation was found in solution. These distinct aggregation behaviors can be explained by the different orientations of the dyes at the interface, as revealed from the analysis of polarization-resolved experiments, the doubly-charged dyes lying more flat on the interface than the singly charged ones. Although YOYO-1 and YOPRO-1 do not form H-dimer/aggregates at the interface, time-resolved SSHG measurements point to the occurrence of intra- and intermolecular interactions, respectively, which inhibit the ultrafast non-radiative decay of the excited dyes via large amplitude motion, and lead to a nanosecond excited-state lifetime. The distinct behavior evidenced here for YOYO-1 and YOSAC dyes points to their potential use as fluorescent or SHG interfacial probes.
In numerical simulations, based on frozen-density embedding theory, the independent variables describing the total system are the embedded wave function (ΨA) and the density  ρB(r)  representing the environment. Due to inhomogeneity of the non-electrostatic component of the total energy:  EnadxcT[ρA,ρB] ≠  ρA(r)  (δEnadxcT[ρA,ρB] / δρA(r))  dr   , the expectation value of the embedding potential is not equal to the corresponding component of the total energy. The differences  ΔnadxcT  = EnadxcT[ρA,ρB] –   ρA(r)  (δEnadxcT[ρA,ρB] / δρA(r))  dr are evaluated using local and semi-local approximations for the functional  EnadxcTA, ρB] in two model systems representing embedded species weakly interacting with the environment. It is found that ΔnadxcT is typically one order of magnitude smaller than EnadxcTA, ρB] and decreases with the overlap between ρA(r) and ρB(r) . The kinetic- and exchange-correlation contributions to ΔnadxcT cancel partially reducing its magnitude to mHartrees. Compared to local approximation for EnadxcTA, ρB], the inhomogeneity is more pronounced in semi-local functionals.
Size-controlled nanocrystals (140 nm and 670 nm) and microcrystals (2.5 mm) of the three-dimensional oxalate network [Ru(bpy)3][NaCr(ox)3], ox = oxalate, bpy = 2,2’-bipyridine, were prepared by the reverse micelle technique. The photo-physical properties of the [Cr(ox)3]3- chromophores in the nanocrystals at low temperatures are significantly different from those of the same chromophore in 4 mm crystallites prepared by fast precipitation. For the latter, the absorption in the region of the R lines of the 4A2 2E transition is characterized by a sharp doublet. For the nanocrystals the inhomogeneous broadening of the two lines is considerably larger with tails on the low-energy side. Whereas the 4 mm crystallites at low temperatures just show equally sharp emission from the R1 line, the emission intensity from the nanocrystallites is shifted into the low-energy tail. Time resolved fluorescence line narrowing spectra and luminescence decay curves demonstrate that this is due to efficient directional energy migration from the center of the nanocrystals towards the surface
The persistent phosphorescence and thermoluminescence of SrAl2O4:Eu2+:Dy3+ is reported for a variety of different excitation wavelengths and excitation temperatures, to provide new insights in the mechanism of the trapping and detrapping. These measurements reveal that the trapping is strongly dependent on the wavelength and temperature. First, with increasing loading temperature, the thermoluminescence peak shifts to lower temperatures which corresponds to a change of trap population. Secondly, the integrated thermoluminescent intensity increases with increasing loading temperature. All wavelength and temperature dependent experiments indicate that the loading of the traps is a thermally activated processes. Utilizing different wavelengths for loading, this effect can be enhanced or reduced. Furthermore excitation with UV-B-light reveals a tendency for detrapping the phosphor, reducing the resulting thermoluminescent intensity and changing the population of the traps.
The transfer of chirality from one set of molecules to another is fundamental for applications in chiral technology and has likely played a crucial role for establishing homochirality on earth. Here we show that an intrinsically chiral gold cluster can transfer its handedness to an achiral molecule adsorbed on its surface. Solutions of chiral Au38(2-PET)24 (2-PET=2-phenylethylthiolate) cluster enantiomers show strong vibrational circular dichroism (VCD) signals in vibrations of the achiral adsorbate. Density functional theory (DFT) calculations reveal that 2-PET molecules adopt a chiral conformation. Chirality transfer from the cluster to the achiral adsorbate is responsible for the preference of one of the two mirror images. Intermolecular interactions between the adsorbed molecules on the crowded cluster surface seem to play a dominant role for the phenomena. Such chirality transfer from metals to adsorbates likely plays an important role in heterogeneous enantioselective catalysis.
Thiolate-protected gold clusters are promising candidates for imaging applications due to their interesting, size-dependent properties. Their high stability and the ability to functionalize the clusters with biocompatible ligands render the clusters interesting for various imaging techniques such as fluorescence microscopy or second-harmonic generation microscopy. The latter nonlinear optical effect has not yet been observed on this type of ultrasmall nanoparticle. We hereby present second- and third-harmonic generation and multiphoton fluorescence of two thiolate-protected gold clusters: Au25(SCH 2CH2Ph)18 and Au38(SCH2CH2Ph)24. At a fundamental wavelength of 800 nm, the Au38(SCH2CH2Ph)24 cluster is active. In contrast, Au25(SCH2CH2Ph)18 does not yield significant SHG signal. We ascribe this to the center of inversion in the Au25 cluster. Measurements on chiral Au25(capt)18 (capt: captopril) gave an SHG response, supporting this interpretation. We also observed third-harmonic generation at a fundamental wavelength of 1200 nm. At 800 and 1100 nm, the clusters decompose after short illumination time but are stable at illumination at 1200 nm. This may be exploited in combined deep tissue imaging and photothermal heating for theranostics applications
  • Amorphous Nanoparticle Assemblies by Bottom-Up Principles
    A. Cunningham, M. Chekini and T. Burgi
    in "Active Plasmonic Nanomaterials" Luciano de Sio, Pan Stanford, 2015, p101-103
    DOI:10.1201/b18647-4 | Abstract | Article PDF
Self-assembly of plasmonic nanoprticles is a fast, robust, and cheap route to obtain large-scale materials with promising optical properties. Although the materials obtained in this way are usually amorphous, the approach has the advantage that three-dimensional assemblies of small particles can be otained with control of the average distance at the nanoscale. In this chapter, we will focus on one particular strategy to assemble plasmonic particles that relies on the interplay between charged particles, surfaces, and polyelectrolytes. Several geometries will be discussed with an emphasis on the optical properties that are dictated by the coupling between plasmons in different geometries.
  • Plasmonic coupling between nanostructures: from periodic and rigid to random and flexible systems
    U. Cataldi, R. Caputo, Y. Kurylyak, G. Klein, M. Chekini, C. Umeton and T. Burgi
    in "Active Plasmonic Nanomaterials" Luciano De Sio, Pan Stanford, 2015, p363-365
    DOI:10.1201/b18647-13 | Abstract | Article HTML | Article PDF
In this chapter, the mechanism of plasmonic coupling of the near-fields that takes place when nanostructure are very close to each other is described. After a theoretical introduction illustrating the main physical principles governing plasmonic coupling, several experimental systems are considered. Interestingly, experimnetal results show that both periodic and rigid, random, and flexible systems of gold nanoparticles exhibit a universal scaling behaviour and verify the plamonic ruler equation.
We have carried out an experiment on a flexible polymeric substrate, coated with a monolayer of gold nanoparticles, which demonstrates how the combined effect of nanoparticle growth and stretching influences the average normalized gap between particles, thus modifying the extinction spectra of the sample. The study paves the way for the realization of a plasmonic strain sensor based on the plasmonic coupling of gold nanoparticles deposited onto elastomeric films: application of a mechanical stretching induces a change of colour of the device and a fine control of the applied strain allows a continuous tuning of the colour.
Elongated plasmonic nanoparticles show superior optical properties when compared to spherical ones. Facile, versatile and cost-effective bottom-up approaches for fabrication of anisotropic nanoparticles in solution have been developed. However, fabrication of 2-D plasmonic templates from elongated nanoparticles with spatial arrangement at the surface is still a challenge. We used controlled seed-mediated growth in the presence of porous and functionalized surface of flexible polydimethylsiloxane (PDMS) templates to provide directional growth and formation of elongated gold nanoparticles (AuNPs). Atomic force microscopy (AFM) and spectroscopy revealed embedding of the particles within the functionalized porous surface of PDMS. Nanoparticles shapes were observed with transmission electron microscope (TEM), UV–Vis spectroscopy, and X-ray powder diffraction (XRPD) measurements, which revealed an overall orientation of particles at the surface. Anisotropic and oriented particles on a flexible substrate are of interest for sensing applications.
  • Fluorescence enhancement in large-scale self-assembled gold nanoparticle double arrays
    M. Chekini, R. Filter, J. Bierwagen, A. Cunningham, C. Rockstuhl and T. Brgi
    Journal of Applied Physics, 118 (23) , 2015, p233107
    DOI:10.1063/1.4938025 | unige:79113 | Abstract | Article HTML | Article PDF
Localized surface plasmon resonances excited in metallic nanoparticles confine and enhance electromagnetic fields at the nanoscale. This is particularly pronounced in dimers made from two closely spaced nanoparticles. When quantum emitters, such as dyes, are placed in the gap of those dimers, their absorption and emission characteristics can be modified. Both processes have to be considered when aiming to enhance the fluorescence from the quantum emitters. This is particularly challenging for dimers, since the electromagnetic properties and the enhanced fluorescence sensitively depend on the distance between the nanoparticles. Here, we use a layer-by-layer method to precisely control the distances in such systems. We consider a dye layer deposited on top of an array of goldnanoparticles or integrated into a central position of a double array of goldnanoparticles. We study the effect of the spatial arrangement and the average distance on the plasmon-enhanced fluorescence. We found a maximum of a 99-fold increase in the fluorescence intensity of the dye layer sandwiched between two goldnanoparticle arrays. The interaction of the dye layer with the plasmonic system also causes a spectral shift in the emission wavelengths and a shortening of the fluorescence life times. Our work paves the way for large-scale, high throughput, and low-cost self-assembled functionalized plasmonic systems that can be used as efficient light sources.
Attached to electron-rich aromatic systems, sulfides are very weak acceptors; however, attached to electron-poor aromatics, they turn into quite strong donors. Here, we show that this underappreciated dual nature of sulfides deserves full consideration for the design of functional systems. Tested with newly designed and synthesized planarizable push−pull mechanophores, sulfide acceptors in the twisted ground state are shown to prevent oxidative degradation and promote blue-shifting deplanarization. Turned on in the planar excited state, sulfide donors promote red-shifting polarization. Impressive Stokes shifts are the result. Demonstrating the usefulness of time-resolved broadband emission spectra to address significant questions, direct experimental evidence for the ultrafast (3.5 ps), polarity-independent and viscosity-dependent planarization from the twisted Franck−Condon S1 state to the relaxed S1 state could be secured.
  • Structure-Property Studies of P-Triarylamine-Substituted Dithieno[3,2-b:2',3'-d]phospholes
    H. Puntscher, P. Kautny, B. Stoeger, A. Tissot, C. Hametner, H. Hagemann, J. Frhlich, T. Baumgartner and D. Lumpi
    RSC Advances, 5 (114) , 2015, p93797-93807
    DOI:10.1039/C5RA13651B | unige:77112 | Abstract | Article HTML | Article PDF
The synthesis of 10 novel P-substituted dithienophosphole oxide compounds applying phenylcarbazole and indolocarbazole donors is presented. Based on photo-physical and theoretical investigations, the study reveals that the pyramidal geometry of the phosphorus allows for the synthesis of charge transfer materials by introducing strong exocyclic donor groups but suppresses intramolecular charge transfer below a certain donor strength threshold, which is an appealing structural feature for the design of donor–acceptor materials. The triplet energies of the phenylcarbazole based compounds are in the range of 2.49–2.65 eV, sufficiently high for potential applications as host materials in PhOLEDs. By contrast, the introduction of indolocarbazole, the weakest employed donor, yields materials exhibiting a significantly higher triplet energy of up to 2.87 eV and a remarkably low singlet–triplet splitting (0.18 eV). In addition an interesting example of an intramolecular electronic through-space interaction has been observed for the ortho-linked phenylcarbazole derivative.
Other than lowest-energy stationary embedded wave functions obtained in Frozen-Density Embedding Theory (FDET) [T. A. Wesolowski, Phys. Rev. A 77, 012504 (2008)] can be associated with electronic excited states but they can be mutually non-orthogonal. Although this does not violate any physical principles — embedded wave functions are only auxiliary objects used to obtain stationary densities — working with orthogonal functions has many practical advantages. In the present work, we show numerically that excitation energies obtained using conventional FDET calculations (allowing for non-orthogonality) can be obtained using embedded wave functions which are strictly orthogonal. The used method preserves the mathematical structure of FDET and self-consistency between energy, embedded wave function, and the embedding potential (they are connected through the Euler-Lagrange equations). The orthogonality is built-in through the linearization in the embedded density of the relevant components of the total energy functional. Moreover, we show formally that the differences between the expectation values of the embedded Hamiltonian are equal to the excitation energies, which is the exact result within linearized FDET. Linearized FDET is shown to be a robust approximation for a large class of reference densities.
  • ChemInform Abstract: A Mild and Efficient CH2-Extrusion Reaction for the Enantiospecific Synthesis of Highly Configurationally Stable Troeger Bases.
    S.A. Pujari, C. Besnard, T. Buergi and J. Lacour
    ChemInform, 46 (43) , 2015
    DOI:10.1002/chin.201543111 | unige:76521 | Abstract | Article HTML | Article PDF
Oxidation of ethano-Troeger bases (I) and (III) with DDQ in wet nitromethane results in a highly enantiospecific methylene extrusion to afford ring contracted products (II) and (IV) which are significantly more configurationally stable than regular Troeger bases.
The ionophore (salph)Co(III)OAc is used here for the first time as a recognition molecule for nitrite in lipophilic membranes. The nature of the recognition process is evaluated by UV-Vis, ATR-IR and potentiometry, while the purity of the compound is confirmed by LC-MS and cyclic voltammetry. Experimental evidence suggests a replacement of the acetate ligand by nitrite. The formation constant between (salph)Co(III)OAc and NO2, β∼108, is estimated potentiometrically with the sandwich membrane method. The analytical parameters, LOD∼3 μM, linear range of four orders of magnitude, stability over four days, and the selectivity over chloride (log KNO2,ClPOT∼-4.1) are similar to previous ionophores for the same ion. Undiluted urine samples were spiked with incremental concentrations of nitrite to characterize the matrix effect. Beyond the observed analytical performance, we aim here to offer a rational study to understand an unconventional charged ionophore recognition process.
  • Pd2Au36(SR)24 cluster: structure studies
    B. Zhang, S. Kaziz, H. Li, D. Wodka, S. Malola, O.V. Safonova, M. Nachtegaal, C. Mazet, I. Dolamic, J. Llorca, E. Kalenius, L.M. Lawson Daku, H. Hkkinen, T. Buergi and N. Barrabes
    Nanoscale, 7 (40) , 2015, p17012-17019
    DOI:10.1039/C5NR04324G | unige:75923 | Abstract | Article HTML | Article PDF | Supporting Info
The location of the Pd atoms in Pd2Au36(SC2H4Ph)24, is studied both experimentally and theoretically. X-ray photoelectron spectroscopy (XPS) indicates oxidized Pd atoms. Palladium K-edge extended X-ray absorption fine-structure (EXAFS) data clearly show Pd-S bonds, which is supported by far infrared spectroscopy. By comparing theoretical EXAFS spectra in R space and circular dichroism spectra of the staple, surface and core doped structures with experimental spectra.
Among the different potential hydrogen storage materials, borohydrides have been largely investigated because of their high gravimetric and volumetric hydrogen content. In the analysis of borohydrides, vibrational spectroscopy plays an important role since it gives information on the local structure of the BH4 ion inside the solid. Here the GF method, developed by Wilson, is used in order to determine the local symmetry of BH4 in solid borohydrides starting from their vibrational spectra. Two different cases of deformations of BH4 are considered. In the first case, the effects of small angular variations on the vibrational spectra of borohydrides will be taken into account; starting from the splitting of the bands corresponding to the deformation modes, the angular deformations will be estimated. In the second one, the BH4 under chemical pressure (in different cubic alkali halides) is considered; in this case, the symmetry of the BH4 remains Td, while the bond lengths change according to the pressure experienced. Different practical examples will be illustrated.
The gold–sulphur interface of self-assembled monolayers (SAMs) was extensively studied some time ago. More recently tremendous progress has been made in the preparation and characterization of thiolate-protected gold clusters. In this feature article we address different properties of the two systems such as their structure, the mobility of the thiolates on the surface and other dynamical aspects, the chirality of the structures and characteristics related to it and their vibrational properties. SAMs and clusters are in the focus of different communities that typically use different experimental approaches to study the respective systems. However, it seems that the nature of the Au–S interfaces in the two cases is quite similar. Recent single crystal X-ray structures of thiolate-protected gold clusters reveal staple motifs characterized by gold ad-atoms sandwiched between two sulphur atoms. This finding contradicts older work on SAMs. However, newer studies on SAMs also reveal ad-atoms. Whether this finding can be generalized remains to be shown. In any case, more and more studies highlight the dynamic nature of the Au–S interface, both on flat surfaces and in clusters. At temperatures slightly above ambient thiolates migrate on the gold surface and on clusters. Evidence for desorption of thiolates at room temperature, at least under certain conditions, has been demonstrated for both systems. The adsorbed thiolate can lead to chirality at different lengths scales, which has been shown both on surfaces and for clusters. Chirality emerges from the organization of the thiolates as well as locally at the molecular level. Chirality can also be transferred from a chiral surface to an adsorbate, as evidenced by vibrational spectroscopy.
  • Modulation of Active Sites in Supported Au38(SC2H4Ph)24 Cluster Catalysts: Effect of Atmosphere and Support Material
    B. Zhang, S. Kaziz, H. Li, M. Gonzalez Hevia, D. Wodka, C. Mazet, T. Brgi and N. Barrabs Rabanal
    The Journal of Physical Chemistry C, 119 (20) , 2015, p11193-11199
    DOI:10.1021/jp512022v | unige:72892 | Abstract | Article HTML | Article PDF
We investigate the distinctly different interaction of thiolate-protected cluster Au38(SC2H4Ph)24with two diverse support materials Al2O3 and CeO2. The catalytic surfaces have been heated in different atmospheres, and the removal of the thiolate ligands has been studied. Thermogravimetry (TG), temperature-programmed process coupled with mass spectrometer (TPRDO-MS), and X-ray absorption spectroscopy (XAFS) studies were performed to understand the desorption of thiol ligands depending on conditions and support material. Depending on the atmosphere and the support material the fate of the thiol ligands is different upon heating, leading to metallic Au in the case of Al2O3 and to cationic Au with CeO2. The thiolate removal seems to be a two-step procedure. The catalytic activity of these Au38-supported clusters was studied for the aerobic oxidation of cyclohexane. Conversion was higher for the gold clusters supported on CeO2. Surprisingly, a significant amount of cyclohexanethiol was found, revealing the active participation of the thiolate ligand in catalytic reactions. The observation also indicates that breaking and formation of C–S bonds can be catalyzed by the gold clusters.
can be formed during the thermal decomposition of metal borohydrides (M(BH4)x). Halogen ions such as fluoride or chloride can contribute to destabilize the ions. Hydride and fluoride mixed species like will be probable products after hydrogen release from mixed boro-hydride-fluoride or borohydride-borofluoride systems (, ). Various number of isomers are possible for (n = 2–11). DFT calculations were performed on isolated ions of all the possible isomers for (n = 0–3, 9–12), using B3LYP functionals and 6-31G(d,p) basis set. Relative stability, vibrational and NMR spectroscopy of these isomers are discussed and compared with available experimental data.
The dynamics of a moderately exergonic photoinduced charge separation has been investigated by ultrafast time-resolved infrared absorption with the dimethylanthracene/phthalonitrile donor/acceptor pair in solvents covering a broad range of polarity. A distinct spectral signature of an exciplex could be identified in the −C≡N stretching region. On the basis of quantum chemistry calculations, the 4–5 times larger width of this band compared to those of the ions and of the locally excited donor bands is explained by a dynamic distribution of exciplex geometry with different mutual orientations and distances of the constituents and, thus, with varying charge-transfer character. Although spectrally similar, two types of exciplexes could be distinguished by their dynamics: short-lived, “tight”, exciplexes generated upon static quenching and longer-lived, “loose”, exciplexes formed upon dynamic quenching in parallel with ion pairs. Tight exciplexes were observed in all solvents, except in the least polar diethyl ether where quenching is slower than diffusion. The product distribution of the dynamic quenching depends strongly on the solvent polarity: whereas no significant loose exciplex population could be detected in acetonitrile, both exciplex and ion pair are generated in less polar solvents, with the relative population of exciplex increasing with decreasing solvent polarity. These results are compared with those reported previously with donor/acceptor pairs in different driving force regimes to obtain a comprehensive picture of the role of the exciplexes in bimolecular photoinduced charge separation.
We report that anion−π and cation−π interactions can occur on the same aromatic surface. Interactions of this type are referred to as ion pair−π interactions. Their existence, nature, and significance are elaborated in the context of spectral tuning, ion binding in solution, and activation of cell-penetrating peptides. The origin of spectral tuning by ion pair−π interactions is unraveled with energy-minimized excited-state structures: The solvent- and pH-independent red shift of absorption and emission of push–pull fluorophores originates from antiparallel ion pair−π attraction to their polarized excited state. In contrast, the complementary parallel ion pair−π repulsion is spectroscopically irrelevant, in part because of charge neutralization by intriguing proton and electron transfers on excited push–pull surfaces. With time-resolved fluorescence measurements, very important differences between antiparallel and parallel ion pair−π interactions are identified and quantitatively dissected from interference by aggregation and ion pair dissociation. Contributions from hydrogen bonding, proton transfer, π–π interactions, chromophore twisting, ion pairing, and self-assembly are systematically addressed and eliminated by concise structural modifications. Ion-exchange studies in solution, activation of cell-penetrating peptides in vesicles, and computational analysis all imply that the situation in the ground state is complementary to spectral tuning in the excited state; i.e., parallel rather than antiparallel ion pair−π interactions are preferred, despite repulsion from the push–pull dipole. The overall quite complete picture of ion pair−π interactions provided by these remarkably coherent yet complex results is expected to attract attention throughout the multiple disciplines of chemistry involved.
A bimetallic dodecaborate LiNaB12H12 has been successfully synthesized for the first time, through a sintering process of LiBH4, NaBH4 and B10H14. LiNaB12H12 has a cubic Pa-3 space group symmetry at room temperature, and transforms into a high temperature phase with Fm-3m symmetry at 488 K, which is lower than that of Li2B12H12 and Na2B12H12. The ionic conductivity at 550 K reaches 0.79 S/cm, which is approximately 8 times higher than that of Na2B12H12 and 11 times higher than that of Li2B12H12. The Li/Na compositional and thus an induced positional disorder in LiNaB12H12 are suggested to be responsible for the reduced phase transition temperature and the improved super ionic conductivity compared to its monometallic counterparts.
Persistent luminescence of SrAl2O4:Eu2+ has attracted considerable attention due to their high initial brightness, long-lasting time and excellent thermal stability. Here the influence of boric acid on the persistent luminescence and thermal oxidation resistance of SrAl2O4:Eu2+ was investigated in detail. Crystal structural analysis and scanning electron microscopy revealed that with the addition of boron, the unit cell volume decreased and the morphology of the particles became more irregular with sharp edges. Thermogravimetric analysis showed better thermal oxidation resistance accompanied by a change in oxygen vacancy concentration when boron acid is used. Photoluminescence spectra and afterglow decay curves confirm an improved afterglow performance for boron-added SrAl2O4:Eu2+. Thermoluminesence allowed monitoring the changes in the trap states due to the presence of B. Our results imply that the substantial improvement of afterglow performance and the thermal stability in SrAl2O4:Eu2+ can be attributed to the incorporation of boron into the aluminate network.
The fluorescence quantum yield of a red naphthalenediimide dye (rNDI) with amino and Br core substituents has been found to decrease by a factor of almost 2 by going from S1 ← S0 to S2 ← S0 excitation. Time-resolved spectroscopic measurements reveal that this deviation from the Kasha−Vavilov’s rule is due to an ultrafast, < 200 fs, intersystem- crossing (ISC) from the S2 state to the triplet manifold, due to the ππ* → nπ* character of the transition and to the presence of the heavy Br atom. In non-core substituted naphthalenediimide (pNDI), ISC is slower, ∼2 ps, and was found to be reversible on a time scale shorter than that of vibrational cooling. The fluorescence and triplet quantum yields of rNDI, thus, can be substantially changed by a simple variation of the excitation wavelength. 
The femto- to microsecond excited-state dynamics of an electron donor–acceptor–donor triad, consisting of two red core-substituted naphthalenediimides (rNDI) and one colorless naphthalenediimide (pNDI), in solution has been compared to that of a supramolecular surface architecture, constituted of coaxial stacks of rNDI and pNDI and prepared by self-organizing surface initiated polymerization (SOSIP). In the triad, charge separation between an excited rNDI and pNDI takes place in highly polar solvents only and for a subensemble of molecules, around 30%, with a folded conformation. Other processes, such as singlet and triplet excitation energy transfer from pNDI to rNDI and intersystem crossing, are also operative. Additionally, bimolecular symmetry-breaking charge separation upon triplet–triplet annihilation is observed on the microsecond time scale in polar solvent. In the surface architecture, excitation of an rNDI is followed by an ultrafast symmetry breaking-charge separation resulting in a charge-transfer exciton, which either recombines or dissociates into a charge-separated state with the electron and the hole in different stacks. The same charge-separated state can also be populated upon excitation of pNDI, either via a charge-transfer pNDI exciton or after excitation energy transfer to rNDI. Charge recombination in the SOSIP film takes place on a wide range of time scales, ranging from a few picoseconds to several hundreds of microseconds.
The structural phase transitions occurring in a series of perovskite-type complex hydrides based on the tetrahydroborate anion BH4- are investigated by means of in situ synchrotron x-ray powder diffraction, vibrational spectroscopy, thermal methods and ab initio calculations in the solid state. Structural dynamics of the BH4 anion are followed with quasi-elastic neutron scattering. We show that unexpected temperature-induced lattice instabilities in perovskite-type ACa(BH4)3 (A = K, Rb, Cs) have their origin in close hydridic di-hydrogen contacts. The rich lattice dynamics lead to coupling between internal B-H vibrations and phonons, resulting in distortions in the high-temperature polymorph that are identical in symmetry to well-known instabilities in oxide perovskites, generally condensing at lower temperatures. It is found that anion-substitution BH4-  ↔ X- (X = Halide) can relax distortions in ACa(BH4)3 by eliminating coulomb repulsive H- • • • H- effects. The interesting nature of phase transition in ACa(BH4)3 enters an unexplored field of weak interactions in ceramic-like host lattices and is the principal motivation for this study. Close di-hydrogen contacts suggest new concepts to tailor crystal symmetries in complex hydride perovskites in the future.
  • Frozen-Density Embedding Strategy for Multilevel Simulations of Electronic StructureOpen access paper
    T.A. Wesolowski, S. Shedge and X. Zhou
    Chemical Reviews, 115 (12) , 2015, p5891-5928
    DOI:10.1021/cr500502v | unige:74195 | Abstract | Article HTML | Article PDF
1. Introduction  2. Frozen-Density Embedding Theory  3. Extensions and Formalisms Related to FDET  4. Approximations in FDET for Multilevel Simulations  5. Numerical Simulations Using Approximated FDET Embedding Potentials  6. Concluding Remarks
  • Access to Enantioenriched 2,3- and 2,5-Dihydrofurans with a Fully Substituted C2 Stereocenter by Pd-Catalyzed Asymmetric Intermolecular Heck ReactionOpen access paper
    G.M. Borrajo-Calleja, V. Bizet, T. Buergi and C. Mazet
    Chemical Science, 6 (8) , 2015, p4807-4811
    DOI:10.1039/C5SC01460C | unige:74172 | Abstract | Article HTML | Article PDF | Supporting Info
A palladium catalyzed intermolecular asymmetric Heck reaction with cyclic trisubstituted olefins is reported. The use of two different chiral ligands provides access to valuable 2,3- and 2,5-dihydrofurans with a fully substituted C2 stereocenter with high levels of regio- and enantiocontrol.
  • Remote stereoselective deconjugation of α,β-unsaturated esters by simple amidation reactions Open access paper
    M. Vishe, R. Hrdina, A.I. Poblador-Bahamonde, C. Besnard, L. Gune, T. Buergi and J. Lacour
    Chemical Science, 6 (8) , 2015, p4923-4928
    DOI:10.1039/C5SC01118C | unige:74171 | Abstract | Article HTML | Article PDF | Supporting Info
The thermodynamically disfavored isomerization of α,β-unsaturated esters to deconjugated β,γ-unsaturated analogues occurs readily when coupled to an amidation. Within the framework of macrocyclic derivatives, it is shown that 15, 16, and 18 membered macrocycles react with tBuOK and anilines to generate in one-pot the β,γ-unsaturated amides (yields up to 88%). Importantly, single (chiral) diastereomers are isolated (d.r. > 49:1, 1H NMR) irrespective of the size and nature of the rings showing an effective transmission of remote stereochemistry during the isomerization process. CSP-chromatographic resolution and absolute configuration determination by VCD are achieved.
Two donor bridge–acceptor molecules with terminal triarylamine and Ru(bpy)32+ (bpy = 2,2′-bipyridine) redox partners were synthesized and investigated by cyclic voltammetry, optical absorption, luminescence, and transient absorption spectroscopy. The two dyads differ only by the central bridging unit, which was tetramethoxybenzene (tmb) in one case and unsubstituted phenylene (ph) in the other case. Photoirradiation of the Ru(bpy)32+ complex of the two dyads triggers intramolecular electron transfer from the triarylamine to the 3MLCT-excited metal complex, and this process occurs with time constants of 1.5 and 6.8 ns for the tmb- and ph-bridged dyads, respectively. Thermal electron transfer in the reverse direction then leads to disappearance of the photoproduct with a time constant of 10 ns in both dyads. The faster rate of photoinduced charge transfer in the tmb-bridged dyad can be understood in the framework of a hole-tunneling model in which the electron-rich tmb bridge imposes a more shallow barrier than the less electron-rich ph spacer. Until now tmb-based molecular wires have received very little attention, and alkoxy substituents have been mostly used for improving the solubility of oligo-p-phenylene vinylene (OPV) and oligo-p-phenylene ethynylene (OPE) wires. Our study illustrates how four alkoxy-substituents on a phenylene backbone can have a significant influence on the charge-transfer properties of a molecular wire, and this is relevant in the greater context of a future molecular electronics technology.
A novel CH2-extrusion reaction leading to the transformation of ethano-Tröger bases into disubstituted methano derivatives is reported (yields up to 93 %). Under mild and metal-free oxidative conditions, a loss of CH2 and a ring contraction are provoked. Despite two bond cleavages at stereogenic nitrogen and carbon centers and a temporary rupture of the bicyclic structure, a very high enantiospecificity (es≥98 %) is observed for this unusual reaction.
  • Excited state interactions between the chiral Au38L24 cluster and covalently attached porphyrin
    B. Varnholt, R. Letrun, J.J. Bergkamp, Y. Fu, O. Yushchenko, S. Decurtins, E. Vauthey, S.-X. Liu and T. Buergi
    Phys. Chem. Chem. Phys., 17 , 2015, p14788-14795
    DOI:10.1039/C5CP01638J | unige:73046 | Abstract | Article PDF | Supporting Info
A protected S-acetylthio porphyrin was synthesized and attached to the Au38(2-phenylethanethiolate)24 cluster in a ligand exchange reaction. Chiral high performance liquid chromatography of the functionalized cluster yielded enantiomeric pairs of clusters probably differing in the binding site of the porphyrin. As proven by circular dichroism, the chirality was maintained. Exciton coupling between the cluster and the chromophore is observed. Zinc can be incorporated into the porphyrin attached to the cluster, as evidence by absorption and fluorescence spectroscopy, however, the reaction is slow.Quenching of the chromophores fluorescence is observed, which can be explained by energy transfer from the porphyrin to the cluster. Transient absorption spectra on the Au38(2-phenylethanethiolate)24 and the functionalized cluster probe the bleach of the gold cluster due to ground state absorption and characteristic excited state absorption signals. Zinc incorporation does not have a pronounced effect on the photophysical behaviour. Decay times are typical for the molecular behaviour of small monolayer protected gold clusters.
  • Electron-deficient fullerenes in triple-channel photosystems
    J. Lpez-Andarias, A. Bolag, C. Nanoz, E. Vauthey, C. Atienza, N. Sakai, N. Martn and S. Matile
    ChemComm, 51 (35) , 2015, p7543-7545
    DOI:10.1039/C5CC01551K | unige:55656 | Abstract | Article HTML | Article PDF | Supporting Info
Fullerenes of increasing electron deficiency are designed, synthesized and evaluated in multicomponent surface architectures to ultimately build gradients in LUMO levels with nine components over 350 meV down to −4.22 eV.
  • Structural, Photophysical and Magnetic Properties of Transition Metal Complexes Based on the Dipicolylamino-chloro-1,2,4,5-tetrazine Ligand
    I. Nazarenko, F. Pop, Q. Sun, A. Hauser, F. Lloret, M. Julve, A. El-Ghayoury and N. Avarvari
    Dalton Transactions, 44 (19) , 2015, p8855-8866
    DOI:10.1039/c5dt00550g | unige:72655 | Abstract | Article HTML | Article PDF | Supporting Info
The ligand 3-chloro-6-dipicolylamino-1,2,4,5-tetrazine (Cl-TTZ-dipica) 1, prepared by the direct reaction between 3,6-dichloro-1,2,4,5-tetrazine and di(2-picolyl)-amine, afforded a series of four neutral transition metal complexes formulated as [Cl-TTZ-dipica-MCl2]2, with M = Zn(II) 2a, Cd(II) 2b, Mn(II) 2c and Co(II) 2d, when reacted with the corresponding metal chlorides. The dinuclear structure of the isostructural complexes was disclosed by single crystal X-ray analysis, clearly indicating the formation of [MII-(m-Cl)2MII] motifs and the involvement of the amino nitrogen atom in semi-coordination with the metal centers, thus leading to distorted octahedral coordination geometries. Moreover, the chlorine atoms, either coordinated to the metal or as substituent on the tetrazine ring, engage respectively in specific anion-p intramolecular and intermolecular interactions with the electron poor tetrazine units in the solid state, thus controlling the supramolecular architecture. Modulation of the emission properties is observed in the case of the Zn(II) and Cd(II) complexes when compared to the free ligand. A striking difference is observed in the magnetic properties of the Mn(II) and Co(II) complexes. An antiferromagnetic coupling takes place in the dimanganese(II) compound (J = -1.25 cm-1) while the Co(II) centers are ferromagnetically coupled in the corresponding complex (J = +0.55 cm-1), the spin Hamiltonian being defined as H = -JSA.SB.
  • Analysis of first order reversal curves in the thermal hysteresis of spin-crossover nanoparticles within the mechanoelastic model
    L. Stoleriu, A. Stancu, P. Chakraborty, A. Hauser and C. Enachescu
    Journal of Applied Physics, 117B , 2015, p307
    DOI:10.1063/1.4914953 | unige:55062 | Article HTML | Article PDF
The recently obtained spin-crossover nanoparticles are possible candidates for applications in the recording media industry as materials for data storage, or as pressure and temperature sensors. For these applications, the intermolecular interactions and interactions between spin-crossover nanoparticles are extremely important, as they may be essential factors in triggering the transition between the two stable phases: the high-spin and low-spin ones. In order to find correlations between the distributions in size and interactions and the transition temperatures distribution, we apply the FORC (First Order Reversal Curves) method, using simulations based on a mechanoelastic model applied to 2D triangular lattices composed of molecules linked by springs and embedded in a surfactant. We consider two Gaussian distributions: one is the size of the nanoparticles and another is the elastic interactions between edge spin-crossover molecules and the surfactant molecules. In order to disentangle the kinetic and non-kinetic parts of the FORC distributions, we compare the results obtained for different temperature sweeping rates. We also show that the presence of few larger particles in a distribution centered around much smaller particles dramatically increases the hysteresis width.
  • Discrete polynuclear manganese(II) complexes with thiacalixarene ligands: synthesis, structures and photophysical properties
    Y. Suffren, N. O'Toole, A. Hauser, E. Jeanneau, A. Brioude and C. Desroches
    Dalton Transactions, 44 (17) , 2015, p7991-8000
    DOI:10.1039/C5DT00827A | unige:72656 | Abstract | Article HTML | Article PDF | Supporting Info
The synthesis, crystal structure and photophysical properties of the new compound [Mn4(ThiaSO2)2F][K(18-crown-6)], ThiaSO2 = p-tertbutylsulphonylcalix[4]arene, are presented and compared to the ones of [Mn4(ThiaSO2)2F]K. The strong orange luminescence is attributed to the Mn2+ centred 4T16A1 transition. Its temperature and pressure dependence and quenching by molecular dioxygen are reported. The latter is attributed to energy transfer from the 4T1 state exciting dioxygen to its 1Σ+g state. In the solid state, the quenching is much more efficient in [Mn4(ThiaSO2)2F][K(18-crown-6)] than in [Mn4(ThiaSO2)2F]K. This is attributed to the open pore structure of the former allowing fast diffusion of dioxygen into the crystal lattice.
Single crystals of tetragonal RCuGa3 (R=La, Pr, Nd and Gd), with BaNiSn3 type structure (space group I4 mm), have been grown by high temperature solution growth technique using Ga as flux. Their magnetic properties were determined by heat capacity and the measurement of magnetization and electrical resistivity along [100] and [001] directions. Except LaCuGa3, the compounds order magnetically. PrCuGa3 undergoes a ferromagnetic transition with Curie temperature of 4.6 K. NdCuGa3 shows a bulk magnetic transition at 3.3 K. The data on GdCuGa3 indicate combined characteristics of spin glass and antiferromagnetic behavior at low temperatures. From the Schottky heat capacity data the crystal electric field level energy spectra have been determined. Further we have performed temperature dependent measurements of electron spin resonance (ESR) on GdCuGa3 between 11 K and room temperature. The ESR data indicate an enhancement of magnetic fluctuations associated with spin reorientation and both homogeneous and inhomogeneous thermal broadening of the linewidth.
LNTs are unique 3D structures made only of safe and abundant biomaterials by self-assembly. The current bottleneck for developing applications using LNTs is the lack of an easy technique to pattern them on substrates. We report a method to free-draw single lipid nanotube (LNT) patterns in any shape on surfaces with 1,2-dioleoyl-sn-glycero-3-phosphoethanolamine (DOPE) that takes an inverted hexagonal (HII) phase. We used pre-self-assembled LNTs or HII lipid blocks as a lipid reservoir from which new LNTs were pulled by applying a point load with a micromanipulator. The extreme simplicity of our technique originates from the fundamental nature of DOPE lipids that prefer a HII phase, while all the conventional approaches use PC lipids that form a lamellar phase. By adjusting the surface properties with polyelectrolyte multilayers, the created single LNT objects are able to remain adhered to the surface for over a week. Importantly, it could be shown that two vesicles loaded with caged fluorescent molecules were able to fuse well with a LNT, enabling diffusive transport of uncaged fluorescent molecules from one vesicle to the other.
In this report, “fluorescent flippers” are introduced to create planarizable push–pull probes with the mechanosensitivity and fluorescence lifetime needed for practical use in biology. Twisted push–pull scaffolds with large and bright dithienothiophenes and their S,S-dioxides as the first “fluorescent flippers” are shown to report on the lateral organization of lipid bilayers with quantum yields above 80% and lifetimes above 4 ns. Their planarization in liquid-ordered (Lo) and solid-ordered (So) membranes results in red shifts in excitation of up to +80 nm that can be transcribed into red shifts in emission of up to +140 nm by Förster resonance energy transfer (FRET). These unique properties are compatible with multidomain imaging in giant unilamellar vesicles (GUVs) and cells by confocal laser scanning or fluorescence lifetime imaging microscopy. Controls indicate that strong push–pull macrodipoles are important, operational probes do not relocate in response to lateral membrane reorganization, and two flippers are indeed needed to “really swim,” i.e., achieve high mechanosensitivity.
Size-controlled micro- and nanocrystals of a [Ru(bpy)3][NaCr(ox)3] coordination network are prepared using reverse micelles. Compared with the bulk reference, the 2E emission of the Cr(III) ions indicates an efficient directional energy migration toward the surface of the nanocrystals.
  • Mapping the Ultrafast Changes of Continuous Shape Measures in Photoexcited Spin Crossover Complexes without Long-Range Order
    S.E. Canton, X. Zhang, L.M. Lawson Daku, Y. Liu, J. Zhang and S. Alvarez
    The Journal of Physical Chemistry C, 119 (6) , 2015, p3322-3330
    DOI:10.1021/jp5117189 | unige:46831 | Abstract | Article HTML | Article PDF
Establishing a tractable yet complete reaction coordinate for the spin-state interconversion in d4–d7 transition metal complexes is an integral aspect of controlling the dynamics that govern their functionality. For spin crossover phenomena, the limitations of a single-mode approximation that solely accounts for an isotropic increase in the metal–ligand bond length have long been recognized for all but the simple octahedral monodentate FeII compounds. However, identifying the coupled deformations that also impact on the unimolecular rate constants remains experimentally and theoretically challenging, especially for samples that do not display long-range order or when crystallization profoundly alters the dynamics. Owing to the rapid progress in ultrafast X-ray absorption spectroscopy (XAS), it is now possible to obtain transient structural information in any physical phase with unprecedented details. Using picosecond XAS and DFT modeling, the structure adopted by the photoinduced high-spin state of solvated [Fe(terpy)2]2+ (terpy: 2,2′:6′,2″-terpyridine) has been recently established. Based on these results, the methodology of the continuous shape measure is applied to classify and quantify the short-lived distortion of the first coordination shell. The reaction coordinate of the spin-state interconversion is clearly identified as a double axial bending. This finding sets a benchmark for gauging the influence of first-sphere and second-sphere interactions in the family of FeII complexes that incorporate terpy derivatives. Some implications for the optimization of related photoactive FeII complexes are also outlined.
Characterizing structural distortions in the metastable spin states of d4–d7 transition metal ion complexes is crucial to understand the nature of their bistability and eventually control their switching dynamics. In particular, the impact of the Jahn–Teller effect needs to be assessed for any electronic configuration that could be effectively degenerate, as in e.g. the high-spin (HS) manifold of highly symmetric homoleptic FeII complexes. However, capturing its manifestations remains challenging since crystallization generally alters the molecular conformations and their interconversion. With the rapid progress of ultrafast X-ray absorption spectroscopy, it is now possible to collect data with unprecedented signal-to-noise ratio, opening up for detailed structural characterization of transient species in the homogeneous solution phase. By combining the analysis of picosecond X-ray absorption spectra with DFT simulations, the structure of the photoinduced HS state is elucidated for solvated [Fe(terpy)2]2+ (terpy = 2,2′:6′,2″-terpyridine). This species can be viewed as the average 5B structure in D2 symmetry that originates from a dynamic Jahn–Teller effect in the HS manifold. These results evidence the active role played by this particular instance of vibronic coupling in the formation of the HS state for this benchmark molecule. Ultimately, correlating the interplay between intramolecular and intermolecular degrees of freedom to conformational strain and distortions in real time should contribute to the development of advanced functionalities in transition metal ion complexes.
  • Rigid Urea and Self-Healing Thiourea Ethanolamine Monolayers
    C. Stefaniu, P.-L. Zaffalon, A. Carmine, Q. Verolet, S. Fernandez, T.A. Wesolowski, G. Brezesinski and A. Zumbuehl
    Langmuir, 31 (4) , 2015, p1296-1302
    DOI:10.1021/la5039987 | unige:55058 | Abstract | Article HTML | Article PDF | Supporting Info
A series of long-tail alkyl ethanolamine analogs containing amide-, urea-, and thiourea moieties was synthesized and the behavior of the corresponding monolayers was assessed on the Langmuir–Pockels trough combined with grazing incidence X-ray diffraction experiments and complemented by computer simulations. All compounds form stable monolayers at the soft air/water interface. The phase behavior is dominated by strong intermolecular headgroup hydrogen bond networks. While the amide analog forms well-defined monolayer structures, the stronger hydrogen bonds in the urea analogs lead to the formation of small three-dimensional crystallites already during spreading due to concentration fluctuations. The hydrogen bonds in the thiourea case form a two-dimensional network, which ruptures temporarily during compression and is recovered in a self-healing process, while in the urea clusters the hydrogen bonds form a more planar framework with gliding planes keeping the structure intact during compression. Because the thiourea analogs are able to self-heal after rupture, such compounds could have interesting properties as tight, ordered, and self-healing monolayers.
The absorption spectra of Sm2+ doped in MFX (M=Sr, Ba; X=Cl, Br) crystals were studied within the range of 20,000–35,000 cm−1 as a function of temperature and host. The absorption bands observed were described with a simple model developed by Wood and Kaiser using group theory. The temperature and host dependence on the 7F05D3 Fano resonance lines were investigated. BaFCl:Sm2+ system showed a “normal” 7F05D3 transition at 4 K in spite of similar crystal structure and absorption profile with other MFX hosts. New Fano resonances were observed in the absorption spectra at higher energies (23,000–25,000 cm−1) for all MFX:Sm2+ systems at 4 K which persist up to room temperature. Preliminary energy level calculation showed that these resonance lines involve the interaction between higher excited 5LJ states of 4 f6configuration and 4 f55d1 configuration.
Bis(thiomethyl)- and bis(thiohexyl)-tetrathiafulvalene-bromo-benzothiadiazoles, containing electron donor tetrathiafulvalene (TTF) and electron acceptor benzothiadiazole (BTD) units, have been prepared by Stille coupling reactions between the TTF-SnMe3 precursors and BTD-Br2. In another series of experiments, TTF-acetylene-BTD compounds have been synthesized by Sonogashira coupling between either TTF-acetylenes and BTD-Br2 in low yields, or TTF-iodine and BTD-acetylene in moderate yields. In the compound TTF-C≡C-BTD the TTF and BTD units are coplanar in the solid state, as shown by the single crystal X-ray structure, and there is segregation in the packing between the donor and acceptor units. All the derivatives have good electron donor properties, as determined by cyclic voltammetry measurements, and they can also be reversibly reduced thanks to the presence of the BTD moiety. UV-visible spectroscopy and photophysical investigations show the presence of an intramolecular charge transfer (ICT) band and an emission band originating from the charge transfer. Both the absorption and the emission are modulated by the substitution scheme and the insertion of the acetylenic bridge.
The Hoffman-type coordination compound [Fe(pz)Pt(CN)4]⋅2.6 H2O (pz=pyrazine) shows a cooperative thermal spin transition at around 270 K. Synchrotron powder X-Ray diffraction studies reveal that a quantitative photoinduced conversion from the low-spin (LS) state into the high-spin (HS) state, based on the light-induced excited spin-state trapping effect, can be achieved at 10 K in a microcrystalline powder. Time-resolved measurements evidence that the HS→LS relaxation proceeds by a two-step mechanism: a random HS→LS conversion at the beginning of the relaxation is followed by a nucleation and growth process, which proceeds until a quantitative HS→LS transformation has been reached.
  • Controlling singlet–triplet splitting in carbazole–oxadiazole based bipolar phosphorescent host materials
    P. Kautny, Z. Wu, B. Stger, A. Tissot, E. Horkel, J. Chen, D. Ma, H. Hagemann, J. Frhlich and D. Lumpi
    Organic electronics, 17 , 2015, p216-228
    DOI:10.1016/j.orgel.2014.11.027 | unige:44949 | Article HTML | Article PDF | Supporting Info
A rational molecular design strategy for carbazole–oxadiazole based bipolar host materials was developed to improve the device efficiency of blue phosphorescent organic light-emitting diodes (PHOLED). Steric effects of strategically placed methyl groups led to an increase of triplet energies (o-2MPCzPOXD: 2.66 eV and o-3MPCzPOXD: 2.73 eV versus the initial host material o-PczPOXD: 2.62 eV) while less pronouncedly affecting singlet energies and, therefore, retaining low driving voltages, high power efficiencies and remarkably low efficiency roll-offs in PHOLEDs. The maximum quantum efficiencies (EQE) for blue devices (FIrpic) were significantly raised for o-2MPCzPOXD (13.6%) and o-3MPCzPOXD (11.5%) versus o-PCzPOXD (9.0%) although yielding comparable values for green devices (Ir(ppy)3; 12.9% and 15.4% versus 13.2%). Supported by theoretical calculations a structure–property relationship was established from photo-physical properties, PHOLED performance measurements and structural characterization from single crystal data.
Europium doped crystalline Ba7F12Cl2 phosphors have been prepared at temperatures between 650 and 900 °C using alkali chloride fluxes, yielding both disordered (with the incorporation of small amounts of Na) and ordered crystal modifications. The white emission spectrum excited in the near UV consists roughly of two broad emission bands at ca 450 and 590 nm, as well as weak sharp Eu2+ 4f-4f emission bands around 360 nm. The incorporation of Eu2+ is further studied using EPR spectroscopy on single crystals, and reveals a significant zero field splitting. The emission spectrum can be significantly tuned by varying the excitation wavelength between 300 and 390 nm. Fine tuning may also be achieved by chemical substitutions to form Ba7-xMyF12Cl2-zBrz (M = Na, Ca,Eu). Quantitative measurements of the light produced using commercial near UV LEDs show that the color temperature ranges between 4000 and 9700 K with CIE chromaticity coordinates close to the ideal values of x=y=0.333. The best color rendering index (CRI) found was 0.83, and the highest light to light conversion yield was 171 lumen/W. These results show that the title compound is a very promising candidate for white light generation using near UV LED excitation.
Borohydrides are actively considered as potential hydrogen storage materials. In this context fundamental understanding of breaking and forming B-H bond is essential. Isotope exchange reactions allow isolating some parts of this reaction without introducing major structural or chemical changes. Experiments were performed on Ca(BH4)2and Ca(BD4)2 as a function of temperature and pressure. A complete exchange can be realized in about 9h at 200 °C using a deuterium pressure of 20 bar. The activation energy, estimated using first order kinetics, for the forward reaction (Ca(BH4)2 → Ca(BD4)2) was found to be 82.1 ± 2.7 kJ/mol (P = 35 bar) and the one for the backward reaction (Ca(BD4)2 → Ca(BH4)2) was found to be 98.5 ± 8.3 kJ/mol (P = 35 bar). Pressure dependent study shows that the reaction rate increases with increasing pressure up to 35 bar. This behavior is consistent with first adsorption step prior to diffusion into the solid and isotope exchange according to the scheme described below.
The excited-state dynamics of two molecular dyads, consisting of zinc (1) and free-base (2) porphyrin connected via a peptide linker to a core-substituted naphthalenediimide (NDI) have been investigated using optical spectroscopy. These dyads exhibit rich photophysics because of the large number of electronic excited states below 3 eV. In the case of 1 in apolar solvents, excitation energy transfer from the vibrationally hot singlet excited porphyrin to the NDI takes place with a 500 fs time constant. Electronic energy ends up in the NDI-localized triplet state, which decays to the ground state on a microsecond timescale. In polar solvents, ground-state recovery is faster by 5 orders of magnitude because of the occurrence of charge separation followed by recombination. On the other hand, excitation energy transfer in 2 takes place in the opposite direction, namely from the NDI to the porphyrin, which then undergoes intersystem crossing to the triplet state, followed by triplet energy transfer back to the NDI. Therefore, four distinct local electronic excited states are consecutively populated after excitation of the NDI unit of 2, with the energy shuttling between the two ends of the dyad.
  • Substituent and Solvent Effects on the Excited State Deactivation Channels in Anils and Boranils
    J. Dobkowski, P. Wnuk, J. Buczynska, M. Pszona, G. Orzanowska, D. Frath, G. Ulrich, J. Massue, S. Mosquera-Vzquez, E. Vauthey, C. Radzewicz, R. Ziessel and J. Waluk
    Chemistry - A European Journal, 21 (3) , 2015, p1312-1327
    DOI:10.1002/chem.201404669 | unige:44951 | Abstract | Article HTML | Article PDF | Supporting Info
Differently substituted anils (Schiff bases) and their boranil counterparts lacking the proton-transfer functionality have been studied using stationary and femtosecond time-resolved absorption, fluorescence, and IR techniques, combined with quantum mechanical modelling. Dual fluorescence observed in anils was attributed to excited state intramolecular proton transfer. The rate of this process varies upon changing solvent polarity. In the nitro-substituted anil, proton translocation is accompanied by intramolecular electron transfer coupled with twisting of the nitrophenyl group. The same type of structure is responsible for the emission of the corresponding boranil. A general model was proposed to explain different photophysical responses to different substitution patterns in anils and boranils. It is based on the analysis of changes in the lengths of CN and CC bonds linking the phenyl moieties. The model allows predicting the contributions of different channels that involve torsional dynamics to excited state depopulation.
  • Smaller than a nanoparticle with the design of discrete polynuclear molecular complexes displaying near-infrared to visible upconversion
    D. Zare, Y. Suffren, L. Gune, S.V. Eliseeva, H. Nozary, L. Aboshyan-Sorgho, S. Petoud, A. Hauser and C. Piguet
    Dalton Transactions, 44 (6) , 2015, p2529-2540
    DOI:10.1039/C4DT02336F | unige:46187 | Abstract | Article HTML | Article PDF | Supporting Info
This work shows that the operation of near-infrared to visible light-upconversion in a discrete molecule is not limited to non-linear optical processes, but may result from superexcitation processes using linear optics. The design of nine-coordinate metallic sites made up of neutral N-heterocyclic donor atoms in kinetically inert dinuclear [GaEr(L1)3]6+ and trinuclear [GaErGa(L2)3]9+ helicates leads to [ErN9] chromophores displaying unprecedented dual visible nanosecond Er(4S3/24I15/2) and near-infrared microsecond Er(4I13/24I15/2) emissive components. Attempts to induce one ion excited-state absorption (ESA) upconversion upon near-infrared excitation of these complexes failed because of the too-faint Er-centred absorption cross sections. The replacement of the trivalent gallium cation with a photophysically-tailored pseudo-octahedral [CrN6] chromophore working as a sensitizer for trivalent erbium in [CrEr(L1)3]6+ improves the near-infrared excitation efficiency, leading to the observation of a weak energy transfer upconversion (ETU). The connection of a second sensitizer in [CrErCr(L2)3]9+ generates a novel mechanism for upconversion, in which the superexcitation process is based on the CrIII-sensitizers. Two successive Cr→Er energy transfer processes (concerted-ETU) compete with a standard Er-centred ETU, and a gain in upconverted luminescence by a factor larger than statistical values is predicted and observed.
The electronic absorption spectrum of 3-hydroxyflavone (3HF) in various solvents exhibits a long-wavelength (LW) band, whose origin has been debated. The excited-state dynamics of neutral and basic solutions of 3HF in alcohols upon excitation in this LW band has been investigated using a combination of fluorescence up-conversion and transient electronic and vibrational absorption spectroscopies. The ensemble of results reveals that, in neutral solutions, LW excitation results in the population of two excited species with similar fluorescence spectra but very different lifetimes, namely 40–100 ps and 2–3 ns, depending on the solvent. In basic solutions, the relative concentrations of these species change considerably in favor of that with the short-lived excited state. On the basis of the spectroscopic data and quantum chemistry calculations, the short lifetime is attributed to the excited state of 3HF anion, whereas the long one is tentatively assigned to an excited hydrogen-bonded complex with the solvent. Excited-state intermolecular proton transfer from the solvent to the anion yielding the tautomeric form of 3HF is not operative, as the excited anion decays to the ground state via an efficient nonradiative transition.
  • On the Role of Ligand-Field States for the Photophysical Properties of Ruthenium(II) Polypyridyl Complexes
    Q. Sun, S. Mosquera-Vazquez, Y. Suffren, J. Hankache, N. Amstutz, L.M. Lawson Daku, E. Vauthey and A. Hauser
    Coordination Chemistry Reviews, 282-283 , 2015, p87-99
    DOI:10.1016/j.ccr.2014.07.004 | unige:42120 | Abstract | Article HTML | Article PDF
The role of ligand-field states for the photophysical properties of d6 systems has been discussed in a large number of publications over the past decades. Since the seminal paper by Houten and Watts, for instance, the quenching of the 3MLCT luminescence in ruthenium(II) polypyridyl complexes is attributed to the presence of the first excited ligand-field state, namely a component of the 3T1(t2g5eg1) state, at similar energies. If this state lies above the 3MLCT state, the luminescence is quenched via thermal population at elevated temperatures only. If it lies well below, then the luminescence is quenched down to cryogenic temperatures. In this contribution we present transient absorption spectra on non-luminescent ruthenium polypyridyl complexes such as [Ru(m-bpy)3]2+, m-bpy = 6-methyl-2,2’-bipyridine, in acetonitrile at room temperature, which reveal an ultra-rapid depopulation of the 3MLCT state but a much slower ground state recovery. We propose that in this and related complexes the methyl groups force longer metal-ligand bond lengths, thus resulting in a lowering of the ligand-field strength such that the 3dd state drops to below the 3MLCT state, and that furthermore the population of this state from the 3MLCT state occurs faster than its decay to the ground state. In addition we demonstrate that in this complex the luminescence can be switched on by external pressure, which we attribute to a destabilisation of the ligand-field state by the pressure due to its larger molecular volume compared to the ground state as well as the 3MLCT state.
Over recent years, research on thiolate-protected gold clusters Aum(SR)n has gained significant interest. Milestones were the successful determination of a series of crystal structures (Au102(SR)44, Au25(SR)18, Au38(SR)24, Au36(SR)24, and Au28(SR)20). For Au102(SR)44, Au38(SR)24, and Au28(SR)20, intrinsic chirality was found. Strong Cotton effects (circular dichroism, CD) of gold clusters protected by chiral ligands have been reported a long time ago, indicating the transfer of chiral information from the ligand into the cluster core. Our lab has done extensive studies on chiral thiolate-protected gold clusters, including those protected with chiral ligands. We demonstrated that vibrational circular dichroism can serve as a useful tool for the determination of conformation of the ligand on the surface of the cluster. The first reports on crystal structures of Au102(SR)44 and Au38(SR)24 revealed the intrinsic chirality of these clusters. Their chirality mainly arises from the arrangement of the ligands on the surface of the cluster cores. As achiral ligands are used to stabilize the clusters, racemic mixtures are obtained. However, the separation of the enantiomers by HPLC was demonstrated which enabled the measurement of their CD spectra. Thermally induced inversion allows determination of the activation parameters for their racemization. The inversion demonstrates that the gold–thiolate interface is anything but fixed; in contrast, it is rather flexible. This result is of fundamental interest and needs to be considered in future applications. A second line of our research is the selective introduction of chiral, bidentate ligands into the ligand layer of intrinsically chiral gold clusters. The ligand exchange reaction is highly diastereoselective. The bidentate ligand connects two of the protecting units on the cluster surface and thus effectively stabilizes the cluster against thermally induced inversion. A minor (but significant) influence of chiral ligands to the CD spectra of the clusters is observed. The studied system represents the first example of an intrinsically chiral gold cluster with a defined number of exchanged ligands, full control over their regio- and stereochemistry. The methodology allows for the selective preparation of mixed-ligand cluster compounds and a thorough investigation of the influence of single ligands on the cluster’s properties. Overall, the method enables even more detailed tailoring of properties. Still, central questions remain unanswered: (1) Is intrinsic chirality a ubiquitous feature of thiolate-protected gold clusters? (2) How does chirality transfer work? (3) What are the applications for chiral thiolate-protected gold clusters? In this Account, we summarize the main findings on chirality in thiolate-protected gold cluster of the past half decade. Emphasis is put on intrinsically chiral clusters and their structures, optical activity, and reactivity.
The Au102(p-MBA)44 cluster (p-MBA: para-mercaptobenzoic acid) is observed as a chiral compound comprised of achiral components in its single-crystal structure. So far the enantiomers observed in the crystal structure are not isolated, nor is the circular dichroism spectrum known. A chiral phase transfer method is presented which allows partial resolution of the enantiomers by the use of a chiral ammonium bromide, (−)-1R,2S-N-dodecyl-N-methylephedrinium bromide ((−)-DMEBr). At sufficiently low concentration of (−)-DMEBr, the phase transfer from water to chloroform is incomplete. Both the aqueous and organic phases show optical activity of near mirror image relationship. Differences in the spectra are ascribed to the formation of diastereomeric salts. At high concentrations of (−)-DMEBr, full phase transfer is observed. The organic phase, however, still displays optical activity. We assume that one of the diastereomers has very strong optical activity, which overrules the cancelation of the spectra with opposite sign. Comparison with computations further corroborates the experimental data and allows a provisional assignment of handedness of each fraction.
  • Stacked and Tunable Large-Scale Plasmonic Nanoparticle Arrays for Surface-Enhanced Raman Spectroscopy
    S. Mhlig, D. Cialla, A. Cunningham, A. Mrz, K. Weber, T. Brgi, F. Lederer and C. Rockstuhl
    The Journal of Physical Chemistry C, 118 (19) , 2014, p10230-10237
    DOI:10.1021/jp409688p | unige:94111 | Abstract | Article HTML | Article PDF
Surface-enhanced Raman spectroscopy takes advantage of plasmonic substrates that sustain resonances at tunable frequencies with a reproducibly extraordinary field enhancement. Low-cost and large-scale fabrication of these substrates is further required. Here, we present stacked large-scale arrays of strongly coupled gold nanoparticles as promising candidates for such substrates. These arrays are fabricated by bottom-up techniques that fulfill the aforementioned requirements. The distance between adjacent arrays in the stack is controlled with high precision using a discrete number of monolayers of molecules that enable the spectral position of the plasmonic resonances to be tuned. Although the nanoparticles are randomly arranged in each array, the spatial proximity of the stacked arrays enables a strong coupling among nanoparticles to be achieved in adjacent arrays. The huge field enhancements due to these strongly coupled gold nanoparticles are shown to enhance the Raman signal. We show that effectively the optical response from these stacked arrays and the Raman signals can be understood in a simplifying picture where only an individual nanoparticle dimer is considered. The possibility to tune the plasmonic resonances of the substrate across the visible spectrum makes our material a plasmonic substrate of choice for many applications where light–matter interactions need to be intensified.
  • Growing gold nanoparticles on a flexible substrate to enable simple mechanical control of their plasmonic coupling
    U. Cataldi, R. Caputo, Y. Kurylyak, G. Klein, M. Chekini, C. Umeton and T. Brgi
    Journal of Materials Chemistry C, 2 (37) , 2014, p7927
    DOI:10.1039/C4TC01607F | unige:94112 | Abstract | Article HTML | Article PDF
A simple method is presented to control and trigger the coupling between plasmonic particles using both a growing process of gold nanoparticles (GNPs) and a mechanical strain applied to the elastomeric template where these GNPs are anchored. The large scale samples are prepared by first depositing and then further growing gold nanoparticles on a flexible PDMS tape. Upon stretching the tape the particles move further apart in the direction of the stretching and closer together in the direction perpendicular to it. The synergy between the controlled growth of GNPs and the mechanical strain, leads to a drastic shift of the plasmon band and a color change of the sample. Furthermore, the stretching by only a few percent of the amorphous and initially isotropic sample results in a strong polarization-dependent plasmon shift. At smaller gap sizes between neighboring particles, induced by stretching the PDMS tape, the plasmon shift strongly deviates from the behaviour expected considering the plasmon ruler equation. This shows that multipolar coupling effects significantly contribute to the observed shift. Overall, these results indicate that a macroscopic mechanical strain allows one to control the coupling and therefore the electromagnetic field at the nanoscale.
  • Steroid Receptor RNA Activator (SRA) Modification by the Human Pseudouridine Synthase 1 (hPus1p): RNA Binding, Activity, and Atomic ModelOpen access paper
    T. Huet, F.-A. Miannay, J.R. Patton, S. Thore and P.C. Driscoll
    PLoS ONE, 9 (4) , 2014
    DOI:10.1371/journal.pone.0094610 | unige:36716 | Abstract | Article HTML | Article PDF
The most abundant of the modified nucleosides, and once considered as the “fifth” nucleotide in RNA, is pseudouridine, which results from the action of pseudouridine synthases. Recently, the mammalian pseudouridine synthase 1 (hPus1p) has been reported to modulate class I and class II nuclear receptor responses through its ability to modify the Steroid receptor RNA Activator (SRA). These findings highlight a new level of regulation in nuclear receptor (NR)-mediated transcriptional responses. We have characterised the RNA association and activity of the human Pus1p enzyme with its unusual SRA substrate. We validate that the minimal RNA fragment within SRA, named H7, is necessary for both the association and modification by hPus1p. Furthermore, we have determined the crystal structure of the catalytic domain of hPus1p at 2.0 Å resolution, alone and in a complex with several molecules present during crystallisation. This model shows an extended C-terminal helix specifically found in the eukaryotic protein, which may prevent the enzyme from forming a homodimer, both in the crystal lattice and in solution. Our biochemical and structural data help to understand the hPus1p active site architecture, and detail its particular requirements with regard to one of its nuclear substrates, the non-coding RNA SRA.
Cationic azaoxa[4]helicenes can be prepared in a single step from a common xanthenium precursor by addition of nucleophilic amines under monitored conditions (160 °C, 2 min, MW). The (−)-(M) and (+)-(P) enantiomers can be separated by chiral stationary-phase chromatography. Determination of the absolute configuration and racemization barrier (ΔG (433 K) 33.3 ± 1.3 kcal·mol–1) was achieved by VCD and ECD spectroscopy, respectively.
  • Non-uniform Continuum Model for Solvated Species Based on Frozen-Density Embedding Theory: The Study Case of Solvatochromism of Coumarin 153
    S.V. Shedge, X. Zhou and T.A. Wesolowski
    Chimia, 68 (9) , 2014, p609-614
    DOI:10.2533/chimia.2014.609 | unige:75040 | Abstract
Recent application of the Frozen-Density Embedding Theory based continuum model of the solvent, which is used for calculating solvatochromic shifts in the UV/Vis range, are reviewed. In this model, the solvent is represented as a non-uniform continuum taking into account both the statistical nature of the solvent and specific solute–solvent interactions. It offers, therefore, a computationally attractive alternative to methods in which the solvent is described at atomistic level. The evaluation of the solvatochromic shift involves only two calculations of excitation energy instead of at least hundreds needed to account for inhomogeneous broadening. The present review provides a detailed graphical analysis of the key quantities of this model: the average charge density of the solvent (<ρB>) and the corresponding Frozen-Density Embedding Theory derived embedding potential for coumarin 153.
  • Crystal-clear - The '2014 Most Superlative Crystal Growth Contest' for School Classes
    D. Perret, H. Hagemann, R. Cerny, C. Renner, E. Giannini, L. Gune, C. Besnard, D. Grard and L. Windels
    Chimia, 68 (12) , 2014, p893-895
    DOI:10.2533/chimia.2014.893 | unige:46708 | Article PDF
To celebrate the International Year of Crystallography among the general public, a consortium of chemists, physicists and crystallographers of the University of Geneva organised in Spring 2014 an incentive crystal growth contest for Geneva scholars aged 4 to 19. Starting from a kit containing a salt and user instructions, classes had to prepare a crystal that met specific criteria according to their category of age. The composition of the salt – potassium dihydrogen phosphate (KDP) – was only disclosed to the participants during the final Awards Ceremony. This contest positively exceeded our expectations with almost 100 participating classes (ca. 1800 participants) and 54 specimens received over all categories.
  • Structure and properties of complex hydride perovskite materials
    P. Schouwink, M.B. Ley, A. Tissot, H. Hagemann, T.R. Jensen, L. Smrcok and R. Cern
    Nature Communications, 5 , 2014, p5706
    DOI:10.1038/ncomms6706 | unige:43536 | Abstract | Article HTML
Perovskite materials host an incredible variety of functionalities. Although the lightest element, hydrogen, is rarely encountered in oxide perovskite lattices, it was recently observed as the hydride anion H, substituting for the oxide anion in ​BaTiO3. Here we present a series of 30 new complex hydride perovskite-type materials, based on the non-spherical ​tetrahydroborate anion ​BH4 and new synthesis protocols involving rare-earth elements. Photophysical, electronic and ​hydrogen storage properties are discussed, along with counterintuitive trends in structural behaviour. The electronic structure is investigated theoretically with density functional theory solid-state calculations. BH4-specific anion dynamics are introduced to perovskites, mediating mechanisms that freeze lattice instabilities and generate supercells of up to 16 × the unit cell volume in AB(BH4)3. In this view, homopolar hydridic di-hydrogen contacts arise as a potential tool with which to tailor crystal symmetries, thus merging concepts of molecular chemistry with ceramic-like host lattices. Furthermore, anion mixing ​BH4−←X (X=Cl−, Br, I) provides a link to the known ABX3 halides.
  • Excited State and Injection Dynamics of Triphenylamine Sensitizers Containing a Benzothiazole Electron-Accepting Group on TiO2 and Al2O3 Thin Films
    M. Fakis, P. Hrobrik, O. Yushchenko, I. Sigmundov, M. Koch, A. Rosspeintner, E. Stathatos and E. Vauthey
    The Journal of Physical Chemistry C, 118 (49) , 2014, p28509-28519
    DOI:10.1021/jp509971q | unige:43537 | Abstract | Article HTML | Article PDF
The excited state and electron injection dynamics of three new organic sensitizers, comprising a triphenylamine moiety connected by an ethenylene (C−C double-bond) or ethynylene (C−C triple-bond) π-spacer to an electron-withdrawing benzothiazole bearing a cyanoacrylic acid anchoring group, have been studied using a combination of steady-state and femtosecond-resolved spectroscopies. The measurements were carried out for the three dyes in predominantly neutral and completely deprotonated forms in liquid solutions and bound on nanocrystalline TiO2 and Al2O3 thin films. In addition, quantum-chemical calculations were performed to predict absorption spectra of the sensitizers and their corresponding cation radicals. Time-resolved fluorescence (TRF) measurements on TiO2 indicate that electron injection takes place on a <0.2 ps time scale. Transient electronic absorption (TA) measurements provide evidence for the formation of radical cations not only in dye-sensitized TiO2 films but also in Al2O3 ones. The cation lifetime in Al2O3 is significantly shorter compared to TiO2, indicating a faster recombination of injected electrons with the dye cations. In addition, the ground-state bleach band in dye-sensitized TiO2 films experiences a gradual red-shift, which is indicative of a transient Stark effect. Finally, femtosecond transient absorption measurements in the IR region point to an ultrafast generation of injected electrons for all dyes. A faster recombination of the injected electrons with the dye cations is observed for the sensitizer decorated with auxiliary electron-donating methoxy groups on the triphenylamine moiety.
  • Single Crystal EPR Studies of Radicals Produced by Radiolysis of Organophosphorus Compounds
    M. Geoffroy
    in "Applications of EPR in Radiation Research" Anders Lund - Masaru Shiotani Eds., Springer, 2014, p33-66
    DOI:10.1007/978-3-319-09216-4_2 | unige:42196
The main radical species produced by radiolysis of organophosphorus compounds are described in this chapter. Their identification is generally based on an analysis of the g and hyperfine tensors obtained from EPR experiments performed on irradiated single crystals. Special emphasis is placed on the properties of the 31P hyperfine tensor, which is often decisive in determining the structure of these radicals. Radiogenic species mentioned in the beginning of this review correspond to simple phosphorus-centered radicals (PR2, PR3, PR4, PR3+, and R2PO). Then, more delocalized systems are reported (allylic structures, captodatively stabilized radicals, symmetrical radical ions containing a P–P bond). The effects of radiolysis on compounds containing low-coordinate phosphorus atoms (e.g. phosphaalkenes) are also described as well as the formation of radical pairs in irradiated phosphated sugars. The last part of the chapter deals with metallated radicals formed by radiolysis of metallic complexes M(CO)5P(H)Ph2 (with M = Mo, Cr, W). In some cases, phosphorus-centered radicals are compared with their arsenic analogues. For several systems the focus lies on dynamical effects; this is the case, for example, for the triptycenephosphinyl radical, which undergoes internal rotation around a P–C bond. Molecular rearrangements after radiolysis of some organophosphorus compounds (e.g. diphosphenes) are also reported.
  • Complementary Surface Second Harmonic Generation and Molecular Dynamics Investigation of the Orientation of Organic Dyes at a Liquid/Liquid Interface
    D. Svechkarev, D. Kolodezny, S. Mosquera-Vzquez and E. Vauthey
    Langmuir, 30 (46) , 2014, p13869-13876
    DOI:10.1021/la503121g | unige:43539 | Abstract | Article HTML | Article PDF
The second-order nonlinear response of two dyes adsorbed at the dodecane/water interface was investigated by surface second harmonic generation (SSHG). These dyes consist of the same chromophoric unit, 2-pyridinyl-5-phenyloxazole, with an alkyl chain located at the two opposite ends. The analysis of the polarization dependence of the SSHG intensity as usually performed points to similar tilt angles of the two dyes with respect to the interface but does not give information on the absolute direction. Molecular dynamics (MD) simulations reveal that both dyes lie almost flat at the interface but have opposite orientations. A refined SSHG data analysis with the width of the orientational distribution yields tilt angles that are in very satisfactory agreement with the MD simulations.
Because of their key role in many areas of science and technology, bimolecular photoinduced electron transfer reactions have been intensively studied over the past five decades. Despite this, several important questions, such as the absence of the Marcus inverted region or the structure of the primary reaction product, have only recently been solved while others still remain unanswered. Ultrafast spectroscopy has proven to be extremely powerful to monitor the entire electron transfer process and to access, with the help of state-of-the-art theoretical models of diffusion-assisted reactions, crucial information like e.g. the intrinsic charge separation dynamics beyond the diffusion limit. Additionally, extension of these experimental techniques to other spectral regions than the UV-visible, such as the infrared, has given a totally new insight into the nature, the structure and the dynamics of the key reaction intermediates, like exciplexes and ions pairs. In this perspective, we highlight these recent progresses and discuss several aspects that still need to be addressed before a thorough understanding of these processes can be attained.
  • Copper-Catalyzed Propargylic Substitution of Dichloro Substrates: Enantioselective Synthesis of Trisubstituted Allenes and Formation of Propargylic Quaternary Stereogenic Centers
    H. Li, D. Grassi, L. Gune, T. Brgi and A. Alexakis
    Chemistry - A European Journal, 20 (50) , 2014, p16694-16706
    DOI:10.1002/chem.201404668 | unige:43540 | Abstract | Article HTML | Article PDF
An easy and versatile Cu-catalyzed propargylic substitution process is presented. Using easily prepared prochiral dichloro substrates, readily available Grignard reagents together with catalytic amount of copper salt and chiral ligand, we accessed a range of synthetically interesting trisubstituted chloroallenes. Substrate scope and nucleophile scope are broad, providing generally high enantioselectivity for the desired 1,3-substitution products. The enantioenriched chloroallenes could be further transformed into the corresponding trisubstituted allenes or terminal alkynes bearing all-carbon quaternary stereogenic centers, through the copper-catalyzed enantiospecific 1,1/1,3-substitutions. The two successive copper-catalyzed reactions could be eventually combined into a one-pot procedure and different desired allenes or alkynes were obtained respectively with high enantiomeric excesses.
  • Enantioselective Catalytic Fluorinative Aza-semipinacol Rearrangement
    F. Romanov-Michailidis, M. Pupier, C. Besnard, T. Brgi and A. Alexakis
    Organic Letters, 16 (19) , 2014, p4988-4991
    DOI:10.1021/ol5022355 | unige:41312 | Abstract | Article HTML | Article PDF
An efficient and highly stereoselective fluorinative aza-semipinacol rearrangement is described. The catalytic reaction requires use of Selectfluor in combination with the chiral, enantiopure phosphate anion derived from acid L3. Under optimized conditions, cyclopropylamines A were transformed into β-fluoro cyclobutylimines B in good yields and high levels of diastereo- and enantiocontrol. Furthermore, the optically active cyclobutylimines were reduced diastereoselectively with L-Selectride in the corresponding fluorinated amines C, compounds of significant interest in the pharmacological industry.
Hydrolysis of metal borohydrides in the presence of CO2 has not been studied so far, although carbon dioxide contained in air is known to accelerate hydrogen generation. KBH4 hydrolysis promoted by CO2 gas put through an aqueous solution was studied by time-resolved ATR-FTIR spectroscopy, showing a transformation of BH4 into B4O5(OH)42−, and a drastically accelerated hydrogen production which can be completed within minutes. This process can be used to produce hydrogen on-board from exhaust gases (CO2 and H2O). We found a new intermediate, K9[B4O5(OH)4]3(CO3)(BH4)·7H2O, forming upon hydrolysis on air via a slow adsorption of the atmospheric CO2. The same intermediate can be crystallized from partly hydrolyzed solutions of KBH4 + CO2, but not from the fully reacted sample saturated with CO2. This phase was studied by single-crystal and powder X-ray diffraction, DSC, TGA, Raman, IR and elemental analysis, all data are fully consistent with the presence of the three different anions and of the crystallized water molecules. Its crystal structure is hexagonal, space group P-62c, with lattice parameters a = 11.2551(4), c = 17.1508(8) Å. Formation of the intermediate produces 16 mol of H2 per mole of adsorbed CO2 and thus is very efficient both gravimetrically and volumetrically. It allows also for an elimination of carbon dioxide from exhaust gases.
In analogy to the synthesis of polycrystalline M2NaIO6 (M = Ca, Sr, Ba) by precipitation in water at 90 °C, the title compound was first prepared as a metastable compound. The stable modification of Pb2NaIO6 was obtained by a heat treatment to 400 °C followed by cooling to room temperature. The crystal structure was refined from powder diffraction data [space group P21/c (14), a = 5.9040(2), b = 5.7526(2), c = 10.1104(3) Å, β = 125.341(1)°]. On heating, at ca. 125 °C, a phase transition to a cubic high temperature modification was observed. The crystal structure was refined from XRD data measured at 200 °C [space group Fm3m (225), a = 8.2678(1) Å]. Depending on the precipitation temperature between 90 °C and 0 °C, several metastable modifications were obtained, which can be distinguished by significantly different lattice parameters. The XRD pattern of a powder precipitated at room temperature is pseudocubic. The crystal structure was refined at room temperature in P21/c with a = 5.8201(4), b = 5.8473(4), c = 10.0798(5) Å, β = 125.074(3)°. This modification behaves almost as a cubic lattice on heating as found from XRD and DSC measurements.
Pd2Au36(SC2H4Ph)24 clusters have been prepared, isolated and separated in their enantiomers. Compared to the parent Au38(SC2H4Ph)24 cluster the doping leads to a significant change of the circular dichrosim spectrum, however, the anisotropy factors are of similar magnitude in both cases. Isolation of the enantiomers allowed us to study the racemi-zation of the chiral cluster, which reflects the flexibility of the ligand shell composed of staple motifs. The doping leads to a substantial lowering of the racemization temperature. The change in activation parameters due to the doping may be solely due to modification of the electronic structure.
The compound Ba5I2O12 was synthesized by heating a precipitate of dissolved Ba(OH)2·8H2O and H5IO6. Rb2O was added to increase the crystallite size. The crystal structure was determined from conventional laboratory X-ray diffraction data by using a real-space structure solution approach followed by a Rietveld refinement. No constraints on positions were used. The structure analysis gave an orthorhombic symmetry with a = 19.7474(2) Å, b = 5.9006(1) Å and c = 10.5773(1) Å. The final RBragg value in space group Pnma (62) was 1.0 %. The structure can be described by layers of a metal and iodine arrangement forming almost pentagonal holes. Raman measurements were correlated with the two IO6 octahedra. Two further barium periodate patterns were observed and indexed.
  • Where does the Raman optical activity of [Rh(en)3]3+ come from? Insight from a combined experimental and theoretical approach
    M. Humbert-Droz, P. Oulevey, L.M. Lawson Daku, S. Luber, H. Hagemann and T. Brgi
    Phys. Chem. Chem. Phys., 16 (42) , 2014, p23260-23273
    DOI:10.1039/C4CP02145B | unige:40863 | Abstract | Article HTML | Article PDF
Backscattered Raman optical activity (ROA) spectra are measured for Δ- and Λ-tris-(ethylenediamine)rhodium(III) chloride in aqueous solution. In addition, the spectra of the four possible conformers in the Λ configuration are investigated by ab initio calculations. The Λ(δδδ) conformer is in best agreement with experimental spectra and examined in more details. The two most stable conformers according to the calculations are not compatible with the experimental ROA spectrum. Insights into the origin of observed band intensities are obtained by means of group coupling matrices. The influence of the first solvation shell is explored via an ab initio molecular dynamics simulation. Taking explicit solvent molecules into account further improves the agreement between calculation and experiment. Analysis of selected normal modes using group coupling matrices shows that solvent molecules lead to normal mode rotation and thus contribute to the ROA intensity, whereas the contribution of the Rh can be neglected.
Configurationally stable diaza[4]helicenes have been prepared in two steps by using a particularly facile N–N bond-cleavage reaction. The synthetic procedure uses hydrazine (NH2NH2) for the introduction of a single nitrogen atom. The strategy is general, modular and highly tolerant to functional groups. A mechanistic rationale is proposed for the spontaneous N–N bond-cleavage reaction. The resulting helical quinacridines are dyes that present absorption and emission properties that can be modulated as a function of pH; the pink quinacridine and green protonated forms (pKa ≈ 9.0) display distinct optical features in the near-IR region. Single enantiomers were obtained by chiral stationary phase HPLC resolution. The absolute configurations were assigned by comparison of the ECD spectra of the conjugated acids with those of known dialkylquinacridinium derivatives. A rather high racemization barrier was measured by means of variable-temperature ECD experiments (ΔG = 30.7 ± 4.0 kcal mol–1 at 140 °C).
  • Nonuniform Continuum Model for Solvatochromism Based on Frozen-Density Embedding Theory
    S.V. Shedge and T.A. Wesolowski
    ChemPhysChem, 15 (15) , 2014, p3291-3300
    DOI:10.1002/cphc.201402351 | unige:41527 | Abstract | Article PDF
Frozen-density embedding theory (FDET) provides the formal framework for multilevel numerical simulations, such that a selected subsystem is described at the quantum mechanical level, whereas its environment is described by means of the electron density (frozen density; ρB( r ) ) The frozen density ρB( r ) is usually obtained from some lower-level quantum mechanical methods applied to the environment, but FDET is not limited to such choices for ρB( r ). The present work concerns the application of FDET, in which ρB( r ) is the statistically averaged electron density of the solvent <ρB( r )> . The specific solute–solvent interactions are represented in a statistical manner in <ρB( r )>. A full self-consistent treatment of solvated chromophore, thus involves a single geometry of the chromophore in a given state and the corresponding <ρB( r )>. We show that the coupling between the two descriptors might be made in an approximate manner that is applicable for both absorption and emission. The proposed protocol leads to accurate (error in the range of 0.05 eV) descriptions of the solvatochromic shifts in both absorption and emission.
We report herein on the polymer-crystallization-assisted thiol-ene photosynthesis of an amphiphilic comb/graft DNA copolymer, or molecular brush, composed of a hydrophobic poly(2-oxazoline) backbone and hydrophilic short single-stranded nucleic acid grafts. Coupling efficiencies are above 60% and thus higher as compared with the straight solid-phase-supported synthesis of amphiphilic DNA block copolymers. The DNA molecular brushes self-assemble into sub-micron-sized spherical structures in water as evidenced by light scattering as well as atomic force and electron microscopy imaging. The nucleotide sequences remain functional, as assessed by UV and fluorescence spectroscopy subsequent to isoindol synthesis at the surface of the structures. The determination of a vesicular morphology is supported by encapsulation and subsequent spectroscopy monitoring of the release of a water-soluble dye and spectroscopic quantification of the hybridization efficiency (30% in average) of the functional nucleic acid strands engaged in structure formation: about one-half of the nucleotide sequences are available for hybridization, whereas the other half are hindered within the self-assembled structure. Because speciation between complementary and non complementary sequences in the medium could be ascertained by confocal laser scanning microscopy, the stable self-assembled molecular brushes demonstrate the potential for sensing applications.
Herein, we address the question whether anion–π and cation–π interactions can take place simultaneously on the same aromatic surface. Covalently positioned carboxylate–guanidinium pairs on the surface of 4-amino-1,8-naphthalimides are used as an example to explore push–pull chromophores as privileged platforms for such “ion pair–π” interactions. In antiparallel orientation with respect to the push–pull dipole, a bathochromic effect is observed. A red shift of 41 nm found in the least polar solvent is in good agreement with the 70 nm expected from theoretical calculations of ground and excited states. Decreasing shifts with solvent polarity, protonation, aggregation, and parallel carboxylate–guanidinium pairs imply that the intramolecular Stark effect from antiparallel ion pair–π interactions exceeds solvatochromic effects by far. Theoretical studies indicate that carboxylate–guanidinium pairs can also interact with the surfaces of π-acidic naphthalenediimides and π-basic pyrenes.
  • Direct coupling of carbenium ions with indoles and anilines for the synthesis of cationic π-conjugated dyes
    R. Vanel, F.-A. Miannay, E. Vauthey and J. Lacour
    ChemComm, 50 (81) , 2014, p12169-12172
    DOI:10.1039/C4CC05193A | unige:40250 | Abstract | Article HTML | Article PDF
A C-C bond forming reaction occurs spontaneously between tris-(2,6-dimethoxyphenyl)carbenium ion and indoles / anilines. The carbocation acts both as electrophile and oxidant. Effective cationic π-conjugated dyes are formed resulting in a strong hyper- and bathochromism
  • Excited-State Dynamics of an Environment-Sensitive Push–Pull Diketopyrrolopyrrole: Major Differences between the Bulk Solution Phase and the Dodecane/Water Interface
    S. Richert, S. Mosquera Vazquez, M. Grzybowski, D.T. Gryko, A. Kyrychenko and E. Vauthey
    Journal of Physical Chemistry B, 118 (33) , 2014, p9952-9963
    DOI:10.1021/jp506062j | unige:39940 | Abstract | Article HTML | Article PDF
The excited-state dynamics of a diketopyrrolopyrrole (DPP) derivative with push–pull substituents has been investigated in a variety of solvents and at the dodecane/water and dodecane/heavy-water interfaces using a combination of ultrafast spectroscopic techniques, including transient electronic absorption and time-resolved surface second-harmonic generation. Whereas the photophysics of a nonpolar DPP analogue is mostly independent of the solvent, the fluorescence decay of the push–pull DPP accelerates strongly by going from aprotic to protic solvents. As this effect increases with the polarity and the hydrogen-bond-donating ability of the solvent, it is attributed to the occurrence of H-bond-assisted nonradiative deactivation induced by the charge-transfer character of the excited state that favors the coupling of the molecule to the H-bond network of the solvent. At the dodecane/water interface, the excited-state lifetime is longer by a factor of ca. 20 than that estimated in pure water and increases further by a factor of about 3 when going to the dodecane/heavy-water interface. This isotope effect, that is more than twice as strong as that measured in bulk solutions, and molecular dynamic simulations indicate that the slowing down of the dynamics at the interface cannot be solely ascribed to a reduced accessibility of the DPP molecule to the aqueous phase. The slower excited-state decay is rather assigned to the conjunction of several effects, such as the strengthening of the H-bond network formed by the interfacial water molecules and the lower local polarity of the interfacial region.
By using a polyelectrolyte layer gold nanoparticles have been assembled onto a Ge internal reflection element. Upon illumination with visible and near infrared light a strong infrared absorption has been observed, which can be traced to intervalence band transitions in Ge. This reveals the existence of holes in the Ge near its valence band edge. The switching between bright and dark states is faster than 160 μs and the device acts as an infrared modulator. The effect develops with a peculiar kinetics, which may indicate the development of an interfacial layer between germanium and gold that allows efficient electron transfer upon illumination.
  • Light-induced spin-state switching in the mixed crystal series of the 2D coordination network {[Zn1-xFex(bbtr)3](BF4)2}: optical spectroscopy and cooperative effects
    P. Chakraborty, C. Enachescu, A. Humair, L. Egger, T. Delgado, A. Tissot, L. Gune, C. Besnard, R. Bronisz and A. Hauser
    Dalton Transactions, 43 (47) , 2014, p17786-17796
    DOI:10.1039/C4DT01728E | unige:42340 | Abstract | Article HTML | Article PDF
Depending on the iron(II) concentration, the mixed crystals of {[Zn1-xFex(bbtr)3](BF4)2}∞, bbtr = 1,4-di(1,2,3-triazol-1-yl)butane, 0.01 ≤ x ≤ 1, show macroscopic light-induced bistability between the high-spin and the low-spin state. In the highly diluted system with x = 0.01 and up to x = 0.31, the photoinduced low-spin state always relaxes back to the high-spin state independent of the initial light-induced low-spin fraction. In the highly concentrated mixed crystals with x = 0.67, 0.87 and 1, the strong cooperative effects coupled to a crystallographic phase transition result in light-induced bistability with decreasing critical light-induced low-spin fraction and increasing hysteresis width for increasing iron(II) concentrations. The lower limit for the light-induced bistability is estimated at x ≈ 0.5.
The density of atomic systems is analysed via the Single-Exponential Decay Detector (SEDD). SEDD is a scalar field designed to explore mathematical, rather than physical, properties of electron density. Nevertheless, it has been shown that SEDD can serve as a descriptor of bonding patterns in molecules as well as an indicator of atomic shells [P. de Silva, J. Korchowiec, and T. A. Wesolowski, ChemPhysChem13, 3462 (2012)]. In this work, a more detailed analysis of atomic shells is done for atoms in the Li–Xe series. Shell populations based on SEDD agree with the Aufbau principle even better than those obtained from the Electron Localization Function, which is a popular indicator of electron localization. A link between SEDD and the local wave vector is given, which provides a physical interpretation of SEDD.
Frozen-Density-Embedding Theory (FDET) is a formalism to obtain the upper bound of the ground-state energy of the total system and the corresponding embedded wavefunction by means of Euler-Lagrange equations [T. A. Wesolowski, Phys. Rev. A77(1), 012504 (2008)]. FDET provides the expression for the embedding potential as a functional of the electron density of the embedded species, electron density of the environment, and the field generated by other charges in the environment. Under certain conditions, FDET leads to the exact ground-state energy and density of the whole system. Following Perdew-Levy theorem on stationary states of the ground-state energy functional, the other-than-ground-state stationary states of the FDET energy functional correspond to excited states. In the present work, we analyze such use of other-than-ground-state embedded wavefunctions obtained in practical calculations, i.e., when the FDET embedding potential is approximated. Three computational approaches based on FDET, that assure self-consistent excitation energy and embedded wavefunction dealing with the issue of orthogonality of embedded wavefunctions for different states in a different manner, are proposed and discussed.
Rather than lead to the usual deoxygenation pathway, metal carbenes derived from α-diazo-β-ketoesters undergo three-atom insertions into epoxides using a combination of 1,10-phenanthroline and [CpRu(CH3CN)3][BArF] as the catalyst. Original 1,4-dioxene motifs are obtained as single regio- and stereoisomers. A perfect syn stereochemistry (retention, e.r. up to 97:3) is observed for the ring opening, which behaves as an SN1-like transformation.
  • Improved persistent luminescence of CaTiO3:Pr by fluorine substitution and thermochemical treatment
    S. Yoon, E.H. Otal, A.E. Maegli, L. Karvonen, S.K. Matam, S.G. Ebbinghaus, B. Walfort, H. Hagemann, S. Pokrant and A. Weidenkaff
    Journal of Alloys and Compounds, 613 , 2014, p338-343
    DOI:10.1016/j.jallcom.2014.06.041 | unige:38546 | Abstract | Article HTML | Article PDF
Fluorine-substituted CaTiO3:Pr phosphors were prepared by a solid-state reaction. Rietveld refinements of powder X-ray diffraction patterns revealed that increasing fluorine-substitution leads to the gradual shrinkage of the unit-cell. Enhanced afterglow intensities were observed with fluorine-substitution. Furthermore, the effect of annealing atmosphere was investigated by thermochemical treatment in different atmospheres (Ar, air and NH3). UV-Vis diffuse reflectance spectra and photoluminescence excitation spectra revealed that Pr4+ in the pristine CaTi(O,F)3:Pr phosphor was partially reduced to Pr3+ under NH3 flow leading to an intensity improvement of ca. 450% compared to CaTiO3:Pr. The substantial improvement of afterglow intensity by fluorine substitution and annealing in NH3 is considered to be connected with the generation of oxygen vacancies and the partial reduction of Pr4+ to Pr3+.
The Raman spectra of a series of monolayer-protected gold clusters were investigated with special emphasis on the Au–S modes below 400 cm–1. These clusters contain monomeric (SR-Au-SR) and dimeric (SR-Au-SR-Au-SR) gold–thiolate staples in their surface. In particular, the Raman spectra of [Au25(2-PET)18]0/–, Au38(2-PET)24, Au40(2-PET)24, and Au144(2-PET)60 (2-PET = 2-phenylethylthiol) were measured in order to study the influence of the cluster size and therefore the composition with respect to the monomeric and dimeric staples. Additionally, spectra of Au25(2-PET)18–2x(S-/rac-BINAS)x (BINAS = 1,1′-binaphthyl-2,2′-dithiol), Au25(CamS)18 (CamS = 1R,4S-camphorthiol), and AunBINASm were measured to identify the influence of the thiolate ligand on the Au–S vibrations. The vibrational spectrum of Au38(SCH3)24 was calculated which allows the assignment of bands to vibrational modes of the different staple motifs. The spectra are sensitive to the size of the cluster and the nature of the ligand. Au–S–C bending around 200 cm–1 shifts to slightly higher wavenumbers for the dimeric as compared to the monomeric staples. Radial Au–S modes (250–325 cm–1) seem to be sensitive toward the staple composition and the bulkiness of the ligand, having higher intensities for long staples and shifting to higher wavenumbers for sterically more demanding ligands. The introduction of only one BINAS dithiol has a dramatic influence on the Au–S vibrations because the molecule bridges two staples which changes their vibrational properties completely.
The dynamics of photoinduced electron transfer between polar acceptors and donors has been investigated in apolar solvents using femtosecond-resolved fluorescence spectroscopy. It was found to be ultrafast and to continuously accelerate by varying the excitation wavelength from the maximum to the red edge of the absorption band of the acceptor, the overall difference being as large as a factor 4–5. This violation of the Kasha–Vavilov rule is explained by a correlation between the composition of the acceptor environment and its transition energy, that is, the more donors around an acceptor, the longer its absorption wavelength, and the faster the quenching. Because of preferential solvation, this dependence is already observed at low quencher concentrations. This effect, which requires quenching to be faster than the fluctuations of the environment composition, should be quite general for photoinduced charge transfer processes in low-polarity, viscous, or rigid media, such as those used in organic optoelectronic devices.
The excited-state dynamics of rhodamine 6G (R6G) has been investigated in aqueous solution using ultrafast transient absorption spectroscopy and at the dodecane/water interface using the femtosecond time-resolved surface second harmonic generation (SSHG) technique. As the R6G concentration exceeds ca. 1 mM in bulk water, both R6G monomers and aggregates are excited to a different extent when using pump pulses at 500 and 530 nm. The excited-state lifetime of the monomers is shortened compared to dilute solutions because of the occurrence of excitation energy transfer to the aggregates, which themselves decay nonradiatively to the ground state with a ca. 70 ps time constant. At the dodecane/water interface, both monomers and aggregates contribute to the SSHG signal to an extent that depends on the bulk concentration, the pump and probe wavelengths, and the polarization of probe and signal beams. The excited-state lifetime of the monomers at the interface is of the order of a few picoseconds even at bulk concentrations where it is as large as several nanoseconds. This is explained by the relatively high interfacial affinity of R6G that leads to a large interfacial concentration, favoring aggregation and thus rapid excitation energy transfer from monomers to aggregates.
Inorganic compounds with BH4- ions are the subject of many recent investigations in the context of potential hydrogen storage materials. In this work, Attenuated Total Reflectance Fourier Transform Infrared (ATR-FTIR) spectra of a series of reference and research compounds (including deuterated samples) are collected and made available to the research community.
  • Anisotropic magnetic, transport and thermodynamic properties of novel tetragonal Ce2RhGa12 compound
    S. Nallamuthu, T.P. Rashid, V. Krishnakumar, C. Besnard, H. Hagemann, M. Reiffers and R. Nagalakshmi
    Journal of Alloys and Compounds, 604 , 2014, p379-383
    DOI:10.1016/j.jallcom.2014.03.067 | unige:37941 | Article HTML
We report on a comprehensive study of the magnetization, resistivity and heat capacity on the single crystals of Ce2RhGa12 synthesized using Ga flux. Single crystal X-ray diffraction data confirm the tetragonal Pb/nbm structure of Ce2RhGa12, which is isostructural to Ce2PdGa12. Ce2RhGa12 orders antiferromagnetically at TN = 3.5 K and exhibits anisotropic magnetic behavior, inferred from the magnetization and resistivity data, taken along the two principal crystallographic directions of the crystal, viz., along [100] and [001]. The anisotropic magnetic response of Ce2RhGa12 establishes [001] as the easy axis of magnetization, and a weak meta-magnetic transition is also observed in the magnetic isotherm at 2K along the same axis. A sharp peak in specific heat signals the bulk antiferromagnetic transition at TN = 3.5 K, which shifts to lower temperatures in low applied fields. The electrical resistivity along the two directions shows metallic behavior from 300K down to 1.8K and establishes Ce2RhGa12 as a normal, trivalent cerium compound.
Light-induced excited spin state trapping (LIESST) in iron(II) spin-crossover compounds, i.e., the light-induced population of the high-spin (S=2) state below the thermal transition temperature, was discovered thirty years ago. For irradiation into metal-ligand charge transfer (MLCT) bands of the low-spin (S=0) species the acknowledged sequence takes the system from the initially excited 1MLCT to the high-spin state via the 3MLCT state within ~150 fs, thereby bypassing low-lying ligand-field (LF) states. Nevertheless, these play role, as borne out by the observation of LIESST and reverse-LIESST on irradiation directly into the LF bands for systems with only high-energy MLCT states. Herein we elucidate the ultrafast reverse-LIESST pathway by identifying the lowest energy S=1 LF state as intermediate state with a lifetime of 39 ps for the light-induced high-spin to low-spin conversion on irradiation into the spin-allowed LF transition of the high-spin species in the NIR.
The dynamics of bimolecular photoinduced electron-transfer reactions has been investigated with three donor/acceptor (D/A) pairs in tetrahydrofuran (THF) and acetonitrile (ACN) using a combination of ultrafast spectroscopic techniques, including time-resolved infrared absorption. For the D/A pairs with the highest driving force of electron transfer, all transient spectroscopic features can be unambiguously assigned to the excited reactant and the ionic products. For the pair with the lowest driving force, three additional transient infrared bands, more intense in THF than in ACN, with a time dependence that differs from those of the other bands are observed. From their frequency and solvent dependence, these bands can be assigned to an exciplex. Moreover, polarization-resolved measurements point to a relatively well-defined mutual orientation of the constituents and to a slower reorientational time compared to those of the individual reactants. Thanks to the minimal overlap of the infrared signature of all transient species in THF, a detailed reaction scheme including the relevant kinetic and thermodynamic parameters could be deduced for this pair. This analysis reveals that the formation and recombination of the ion pair occur almost exclusively via the exciplex.
  • Probing the Anisotropic Distortion of Photoexcited Spin Crossover Complexes with Picosecond X‑ray Absorption Spectroscopy
    S.E. Canton, X. Zhang, L.M. Lawson Daku, A.L. Smeigh, J. Zhang, Y. Liu, C.-J. Wallentin, K. Attenkofer, G. Jennings, C.A. Kurtz, D. Gosztola, K. Wrnmark, A. Hauser and V. Sundstrm
    Journal of Physical Chemistry C, 118 (8) , 2014, p4536-4545
    DOI:10.1021/jp5003963 | unige:37983 | Abstract | Article HTML | Article PDF
For numerous spin crossover complexes, the anisotropic distortion of the first coordination shell around the transition metal center governs the dynamics of the high-spin/lowspin interconversion. However, this structural parameter remains elusive for samples that cannot be investigated with crystallography. The present work demonstrates how picosecond X-ray absorption spectroscopy is able to capture this specifi c deformation in the photoinduced high-spin state of solvated [Fe(terpy)2 ]2+ , a complex which belongs to the prominent family of spin crossover building blocks with nonequivalent metal ligand bonds. The correlated changes in FeNAxial , Fe NDistal , and bite angle NDistal Fe NAxial  extracted from the measurements are in very good agreement with those predicted by DFT calculations in D2d  symmetry. The outlined methodology is generally applicable to the characterization of ultrafast nuclear rearrangements around metal centers in photoactive molecular complexes and nanomaterials, including those that do not display long-range order.
The excited-state dynamics of two multichromophoric arrays composed of a naphthalene diimide centre and four zinc or free-base porphyrins substituted on the naphthalene core via aniline bridges has been investigated using a combination of stationary and ultrafast spectroscopies. These pentads act as efficient antennae as they absorb over the whole visible region, with a band around 700 nm, associated with a transition to the S1 state delocalised over the whole arrays, and bands at higher energy due to transitions centred on the porphyrins. In non-polar solvents, population of these porphyrin states is followed by sub-picosecond internal conversion to the S1 state. The existence of a charge-separated state located above the S1 state could enhance this process. The decay of the S1 state is dominated by non-radiative deactivation on the 100 ps timescale, most probably favoured by the small S1-S0 energy gap and the very high density of vibrational states of these very large chromophores. In polar solvents, the charge-separated state lies just below the S1 state. It can be populated within a few picoseconds by a thermally-activated hole transfer from the S1 state as well as via sub-picosecond non-equilibrium electron transfer from vibrationally hot porphyrin excited states. Because of the small energy gap between the charge-separated state and the ground state, charge recombination is almost barrierless and occurs within a few picoseconds. Despite their very different driving forces, charge separation and recombination occur on similar timescales. This is explained by the electronic coupling that differs considerably for both processes.
Retinal is the light-absorbing biochromophore responsible for the activation of vision pigments and light-driven ion-pumps. Nature has evolved molecular tuning mechanisms that significantly shift the optical properties of the retinal pigments to enable their absorption of visible light. Using large-scale quantum chemical calculations at the density functional theory level combined with the frozen density embedding theory approach, we show here how the protein environment of vision pigments tune the absorption of retinal to the 2.3-2.6 eV (480-530 nm) region by electrostatically dominated interactions between the chromophore and the surrounding protein residues. The calculations accurately reproduce the experimental absorption maxima of rhodopsin (2.49 eV/498 nm), and the red, green, and blue color pigments (2.3-2.9 eV/430-530 nm). We further identify key interactions responsible for the red- and blue-shifting effects by mutating the rhodopsin structure in silico, and find that deprotonation of the retinyl is likely to be responsible for the blue shifted absorption in the blue cone vision pigment.
  • Oxadiazole based bipolar host materials employing planarized triarylamine donors for RGB PHOLEDs with low efficiency roll-off
    P. Kautny, D. Lumpi, Y. Wang, A. Tissot, J. Bintinger, E. Horkel, B. Stoeger, C. Hametner, H. Hagemann, D. Ma and J. Frhlich
    Journal of Materials Chemistry C, 2 (11) , 2014, p2069-2081
    DOI:10.1039/c3tc32338b | unige:34399 | Abstract | Article HTML | Article PDF
A series of 6 novel triarylamine-containing oxadiazole compounds (o-PCzPOXD, o-ICzPOXD, o-TPATOXD, o-PCzTOXD, o-ICzTOXD, o-CzTOXD) have been designed, synthesized and characterized concerning applications as host materials in PHOLED devices. To further improve the ortho-linkage concept, the impact of incorporating planarized electron-donating triarylamine (TAA) structures on intramolecular charge transfer was examined. The effect was evaluated for two series of electron-accepting oxadiazole scaffolds, realizing ortho-linkage on the benzene (POXD) and the thiophene (TOXD) core. Thermal analysis shows increased glass-transition temperatures for planarized structures indicating an improved morphological stability. A higher degree of planarization also results in significantly increased singlet and triplet energy values, revealing the impact on the intramolecular charge transfer. Employing the developed materials, red (o-TPATOXD: CEmax: 28.8 cd A-1, EQEmax: 16.9%), green (o-PCzPOXD: CEmax: 62.9 cd A-1, EQEmax: 17.1%) and blue (o-PCzPOXD: CEmax: 29.8 cd A-1, EQEmax: 13.4%) devices were achieved showing remarkably low efficiency roll-off for planarized donors. Hence, this is the first report of efficient blue devices for this specific class of host materials. It is proposed that the results correlate with an increasing ortho-linkage effect and decreasing donor strength of the TAA moiety by planarization and, thus, tackling one of the major challenges in PHOLED research: improving both triplet energy and compound stability.
To access the intrinsic, diffusion free, rate constant of bimolecular photoinduced electron transfer reactions, fluorescence quenching experiments have been performed with 14 donor/acceptor pairs, covering a driving-force range going from 0.6 to 2.4 eV, using steady-state and femtosecond time-resolved emission, and applying a diffusion-reaction model that accounts for the static and transient stages of the quenching for the analysis. The intrinsic electron transfer rate constants are up to 2 orders of magnitude larger than the diffusion rate constant in acetonitrile. Above ~1.5 eV, a slight decrease of the rate constant is observed, pointing to a much weaker Marcus inverted region than those reported for other types of electron transfer reactions, such as charge recombination. Despite this, the driving force dependence can be rationalized in terms of Marcus theory.
  • Vapor pressure measurements of Mg(BH4)2 using Knudsen torsion effusion thermo graphic method
    L.-N.N. Nforbi, A. Talekar, K.H. Lau, R. Chellapa, W.-M. Chien, D. Chandra, H. Hagemann, Y. Filinchuk, J.-C. Zhao and A. Levchenko
    International Journal of Hydrogen Energy, 39 (5) , 2014, p2175-2186
    DOI:10.1016/j.ijhydene.2013.11.071 | unige:33261 | Abstract | Article PDF
The vapor pressure and molecular weight of effusing vapors of α, β, and amorphous Mg(BH4)2 were determined by Torsion-effusion gravimetric method, under dynamic vacuum. A Cahn balance in the system yielded the rate of the weight loss. Molecular weights measured revealed if the effusion was congruent or there was disproportionation. The vaporization behavior of crystalline Mg(BH4)2, was measured up to 533 K at pressures of ∼10−5 torr. It was found that Mg(BH4)2 disproportionates to form predominantly H2 gas (∼95%) with a small amount of Mg(BH4)2 (∼5%) in the gas phase. The combined average molecular weight measured is 4.16 g/mol. The equations for vapor pressures for crystalline Mg(BH4)2 are given by: log PTotal(bar) = 9.2303 − 7286.2/T, log PMg(BH4)2 (bar) = 8.2515 - 7286.2 / , and log PH2 (bar) = 9.1821 - 7286.2 / T. The partial pressures of the gaseous species were determined as PMg2(4BH)(g)/PT=0.105 and PH2(g)/PT=0.895. Enthalpies of vaporization for the effusing gases were calculated to be ΔH = +558.0 kJ/mol H2 and ΔH = +135 kJ/mol Mg(BH4)2. The standard Gibbs free energy changes, ΔG°(kJ/mol), for the complete decomposition reaction (Mg(BH4)2(s) → Mg(s) + 2B(s) + 4H2(g)), sublimation reaction (Mg(BH4)2(s) → Mg(BH4)2(g)) and the disproportionation reaction for Mg(BH4)2 are reported in this paper. The decomposition pathway of amorphous Mg(BH4)2 was also carried out between 388.2 K and 712.8 K showing multistep decomposition of a-Mg(BH4)2 Different reaction products were obtained depending on the method used in the vaporization experiment. The behavior of the amorphous Mg(BH4)2(s) is very different from those for the two crystalline phases (α and β). The vapor pressure behavior and thermodynamics of vaporization of different phases of Mg(BH4)2 are presented.
According to Frozen-Density Embedding Theory, any observable evaluated for the embedded species is a functional of the frozen density (ρB —the density associated with the environment). The environment-induced shifts in the energies of local excitations in organic chromophores embedded in hydrogen-bonded environments are analyzed. The excitation energies obtained for ρB , which is derived from ground-state calculations for the whole environment applying medium quality basis sets (STO–DZP) or larger, vary in a narrow range (about 0.02 eV which is at least one order of magnitude less than the magnitude of the shift). At the same time, the ground-state dipole moment of the environment varies significantly. The lack of correlation between the calculated shift and the dipole moment of the environment reflects the fact that, in Frozen-Density Embedding Theory, the partitioning of the total density is not unique. As a consequence, such concepts as “environment polarization” are not well defined within Frozen-Density Embedding Theory. Other strategies to generate ρB (superposition of densities of atoms/molecules in the environment) are shown to be less robust for simulating excitation energy shifts for chromophores in environments comprising hydrogen-bonded molecules.
A large pi-conjugated chromophore composed of two dipyrido[3,2-a:2’,3’-c]phenazine (dppz) units directly fused to the central tetrathiafulvalene (TTF) core, has been prepared as a bridging ligand, and its strong binding ability to Ru2+ forming a new dinuclear complex is presented. The electronic absorption and luminescence and the electrochemical behaviour of the free ligand as well as the Ru2+ complex have been investigated in detail. The free ligand shows a very strong band in the UV region consistent with ligand centred π-π* transitions and an intense broad band in the visible region corresponding to an intramolecular charge transfer (ILCT) transition. Upon coordination, a metal-to-ligand charge transfer (MLCT) appears at 22520 cm-1 while the ILCT band is bathochromically shifted by 1620 cm-1. These electrochemically amphoteric chromophores have also been characterized by spectroelectrochemical methods. The oxidized radical species of the free ligand show a strong tendency to undergo aggregation, in which long-distance attractive interactions overcome the electrostatic repulsion. Moreover, these two new chromophores reveal an ILCT fluorescence with large solvent-dependent Stokes shifts and quantum efficiencies of 0.052 for the free ligand and 0.016 for its dinuclear Ru2+ complex in CH2Cl2.
  • Discriminability of tryptophan containing dipeptides using quantum control
    S. Afonina, O. Nenadl, A. Rondi, L. Bonacina, J. Extermann, D. Kiselev, I. Dolamic, T. Burgi and J.P. Wolf
    Applied Physics B, 111 (4) , 2013, p541-549
    DOI:10.1007/s00340-013-5370-0 | unige:37054 | Abstract | Article HTML | Article PDF
We show that the coherent manipulation of molecular wavepackets in the excited states of trp-containing dipeptides allows efficient discrimination among them. Optimal dynamic discrimination fails, however, for some dipeptide couples. When considering the limited spectral resources at play (3 nm bandwidth at 266 nm), we discuss the concept of discriminability, which appears uncorrelated to both static spectra and relaxation lifetimes.
  • Model-free Investigation of Ultrafast Bimolecular Chemical Reactions: Bimolecular Photo Induced Electron TransferOpen access paper
    B. Lang, A. Rosspeintner and E. Vauthey
    EPJ Web of Conferences, 41 , 2013, p5041
    DOI:10.1051/epjconf/20134105041 | unige:94113 | Abstract | Article PDF
Using photoinduced bimolecular electron transfer reactions as example we demonstrate how diffusion controlled bimolecular chemical reactions can be studied in a model-free manner by quantitatively combining different ultrafast spectroscopical tools.
Attenuated total reflection infrared (ATR-IR) spectroscopy is used to study the adsorption of gold and silver nanoparticles and the layer-by-layer (LBL) growth of polyelectrolyte multilayers on a Ge ATR crystal. The Ge ATR crystal is first functionalized using positively charged polyelectrolyte poly(allylamine hydrochloride) (PAH). Then citrate-stabilized gold or silver nanoparticles are adsorbed onto the modified Ge ATR crystal. When gold or silver nanoparticles are adsorbed, a drastic increase of the water signal is observed which is attributed to an enhanced absorption of IR radiation near the nanoparticles. This enhancement was much larger for the silver nanoparticles (SNP). On top of the nanoparticles multilayers of oppositely charged polyelectrolytes PAH and poly(sodium 4-styrenesulfonate) (PSS) were deposited, which allowed to study the enhancement of the IR signals as a function of the distance from the nanoparticles. Furthermore, adsorption of a thiol, N-acetyl-l-cysteine, on the nanoparticles confirmed the enhancement. In the case of SNP an absorbance signal of about 15% was observed, which is a factor of about 40 times larger compared to typical signals measure without nanoparticles.
  • Modeling Transition Metal Complexes in the Frameworkof the Spin-Crossover Phenomenon: a DFT Perspective
    L.M. Lawson Daku
    Current Inorganic Chemistry, 3 (3) , 2013, p242-259
    DOI:10.2174/1877944103666140110231029 | unige:73072
Using the study of the low-spin complex [Fe(bpy)3]2+ in the gas phase and in condensed phases as a guideline, we examine different aspects of the application of DFT to the study of transition metal complexes in the framework of spin crossover or related phenomena.
  • Crystal structure solution of an elusive polymorph of Dibenzylsquaramide
    A. Portell, X. Alcob, L.M. Lawson Daku, R. Cerny and R. Prohens
    Powder Diffraction, 28 (S2) , 2013, p470-480
    DOI:10.1017/S0885715613000821 | unige:35159 | Abstract | Article PDF
The crystal structure of the third polymorph of dibenzylsquaramide (Portell, A. et al., 2009), (fig. 1) has been determined from laboratory X-ray powder diffraction data by means of direct space methods using the computing program FOX. (Favre-Nicolin and Černý, 2002) The structure resolution has not been straightforward due to several difficulties on the indexing process and in the space group assignment. The asymmetric unit contains two different conformers, which has implied an additional difficulty during the Rietveld (Rietveld, 1969) refinement. All these issues together with particular structural features of disquaramides are discussed.
  • Near-Infrared to Visible Light-Upconversion in Molecules: From Dream to Reality
    Y. Suffren, D. Zare, S.V. Eliseeva, L. Gune, H. Nozary, T. Lathion, L. Aboshyan-Sorgho, S. Petoud, A. Hauser and C. Piguet
    Journal of Physical Chemistry C, 117 (51) , 2013, p26957-26963
    DOI:10.1021/jp4107519 | unige:34037 | Abstract | Article HTML | Article PDF
Light-upconversion via stepwise energy transfer from a sensitizer to an activator exploits linear optics for converting low-energy infrared or near-infrared incident photons to higher energy emission occurring in the part of the electromagnetic spectrum ranging from visible to ultraviolet. Stepwise excitation is restricted to activators possessing intermediate long-lived excited states such as those found for trivalent lanthanide cations dispersed in solid-state matrices. When the activator is embedded in a molecular complex, efficient non-radiative relaxation processes usually reduce excited state lifetimes to such an extent that upconversion becomes too inefficient to be detected under practical excitation intensities. Theoretical considerations suggest that the combination of millisecond timescale sensitizers with a central lanthanide activator located in supramolecular complexes circumvents this bottleneck by creating a novel pathway reminiscent of the energy transfer upconversion mechanism observed in doped solids. Application of this novel concept to chromium/erbium pairs in discrete triple-stranded helicates demonstrates that strong-field trivalent chromium chromophores irradiated with near-infrared photons produce upconverted green erbium-centered emission both in the solid state and in solution.
  • A Pt(II) complex with both a phenanthroline and a tetrathiafulvalene-extended dithiolate ligand: Synthesis, crystal structure, electro-chemical and spectroscopic properties
    C. Jia, J. Ding, S.-X. Liu, G. Labat, A. Neels, A. Hauser and S. Decurtins
    Polyhedron, 55 , 2013, p87-91
    DOI:10.1016/j.poly.2013.02.064 | unige:32100 | Article HTML | Article PDF
The reaction of 4,5-bis(2'-cyano-ethylsulfanyl)-4',5'-dipropylthiotetrathiafulvalene with [Pt(phen)Cl2] (phen = 1,10-phenanthroline) with CsOH as base in CH3OH–THF affords the target complex 1 in 44% yield. This complex crystallizes in the monoclinic space group P21/c, M = 790.01, a = 12.1732(12), b = 15.851(2), c = 14.5371(16) Å, b = 107.693(12)˚, V = 2672.4(5) Å3 and Z = 4. It undergoes two reversible single-electron oxidation and two irreversible reduction processes. An intense electronic absorption band at 15200 cm-1 (658 nm) in CH2Cl2 is assigned to the intramolecular mixed metal/ligand-to-ligand charge transfer (LLCT) from a tetrathiafulvalene-extended dithiolate-based HOMO to a phenanthroline-based LUMO. This band shifts hypsochromically with increasing solvent polarity. Systematic changes in the optical spectra upon oxidation allow precise tuning of the oxidation states of 1 and reversible control over its optical properties. Irradiation of 1 at 15625 cm-1 (640 nm) in glassy solution below 150 K results in emission from the 3LLCT excited state.
  • Ultrafast Excited-State Dynamics of Donor-Acceptor Biaryls: Comparison between Pyridinium and Pyrylium Phenolates
    R. Letrun, M. Koch, M.L. Dekhtyar, V.V. Kurdyukov, A.I. Tolmachev, W. Rettig and E. Vauthey
    The Journal of Physical Chemistry A, 117 (49) , 2013, p13112-13126
    DOI:10.1021/jp409646g | unige:32101 | Abstract | Article HTML | Article PDF
The excited-state dynamics of two donor–acceptor biaryls that differ by the strength of the acceptor, a pyridinium or a pyrylium moiety, have been investigated using a combination of steady-state solvatochromic absorption, ultrafast fluorescence, as well as visible and infrared transient absorption spectroscopies. The negative solvatochromic behavior of pyridinium phenolate indicates that the permanent electric dipole moment experiences a decrease upon S1 ← S0 excitation, implying that the ground state possesses more zwitterionic character than the excited state. In contrast, pyrylium phenolate exhibits a weakly positive solvatochromic behavior corresponding to a small increase in the dipole moment upon excitation, implying more zwitterionic character in the excited than the ground state. Both compounds are therefore situated at different sides of the cyanine-limit structure, which has equally polar ground and excited states. Despite these differences, both molecules exhibit qualitatively similar excited-state properties. They are characterized by a very short fluorescence lifetime, increasing from about 1 to 20 ps, when varying solvent viscosity from 0.4 to 11 cP. There are, however, characteristic differences between the two compounds: The excited-state lifetimes of the pyrylium dye are shorter and also depend somewhat on polarity. The ensemble of spectroscopic data can be explained with a model where the emitting Franck–Condon excited state relaxes upon twisting around the single bond between the aryl units to a point where the excited- and ground-state surfaces are very close or intersect. After internal conversion to the ground state, the distorted molecule relaxes back to its equilibrium planar configuration, again largely dependent upon solvent viscosity. However, in this case, the kinetics for the pyrylium dye are slower than for the pyridinium dye and the polar solvent-induced acceleration is significantly stronger than in the excited state. This difference of kinetic behavior between the two compounds is a direct consequence of the change of the electronic structure from anormal to an overcritical merocyanine evidenced by steady-state spectroscopy.
  • Excited-State Dynamics of Charged Dyes at Alkane/Water Interfaces in the Presence of Salts and Ionic Surfactants
    M. Fedoseeva, P. Fita and E. Vauthey
    Langmuir, 29 (48) , 2013, p14865-14872
    DOI:10.1021/la402191p | unige:32123 | Abstract | Article HTML | Article PDF
The excited-state dynamics of the cationic dye malachite green (MG) and of the dianionic dye eosin B at the dodecane/water interface has been investigated using femtosecond time-resolved surface second harmonic generation (TR-SSHG). By using different probe wavelengths, the contributions of monomeric and aggregated MG to the signal could be spectroscopically distinguished. The effect of the addition of a small amount of surfactants was found to strongly depend on the relative charges of surfactant and dye. For surfactant/dye pairs with opposite charges, the TR-SSHG signal is dominated by the contribution from aggregates, whereas for pairs with the same charges, the signal intensity becomes vanishingly small. These effects are explained in terms of electrostatic interactions between surfactants and dyes that favor either attraction of the dye toward the interface or its repulsion toward the bulk. As a very similar behavior is observed with MG upon addition of NaSCN, we conclude that, in this case, this effect reflects the affinity of SCN¯ for the interface. On the other hand, the guanidinium cation was found to have a different effect than that of a positively charged surfactant on the SSHG signal of MG, indicating this cation does not accumulate in the interfacial region.
  • Acylgermanes: Photoinitiators and Sources for Ge-Centered Radicals. Insights into their Reactivity
    D. Neshchadin, A. Rosspeintner, M. Griesser, B. Lang, S. Mosquera-Vazquez, E. Vauthey, V. Gorelik, R. Liska, C. Hametner, B. Ganster, R. Saf, N. Moszner and G. Gescheidt
    Journal of the American Chemical Society, 135 (46) , 2013, p17314-17321
    DOI:10.1021/ja404433u | unige:31278 | Abstract | Article HTML | Article PDF
Acylgermanes have been shown to act as efficient photoinitiators. In this investigation we show how dibenzoyldiethylgermane 1 reacts upon photoexcitation. Our real-time investigation utilizes femto- and nanosecond transient absorption, time-resolved EPR (50 ns), photo-chemically induced dynamic nuclear polarization, DFT calculations, and GC-MS analysis. The benzoyldiethylgermyl radical G• is formed via the triplet state of parent 1. On the nanosecond time scale this radical can recombine or undergo hydrogen-transfer reactions. Radical G• reacts with butyl acrylate at a rate of 1.2 ± 0.1 × 108 and 3.2 ± 0.2 × 108 M–1 s–1, in toluene and acetonitrile, respectively. This is ˜1 order of magnitude faster than related phosphorus-based radicals. The initial germyl and benzoyl radicals undergo follow-up reactions leading to oligomers comprising Ge–O bonds. LC-NMR analysis of photocured mixtures containing 1 and the sterically hindered acrylate 3,3-dimethyl-2-methylenebutanoate reveals that the products formed in the course of a polymerization are consistent with the intermediates established at short time scales.
The far infrared spectra of a series of well-defined gold clusters covered by 2-phenylethanetiolate were studied. The spectra of the cluster are different but the differences are subtle. The Au-S stretching vibrations give rise to bands around 300 cm-1 and below. The relative intensity of these bands changes but they shift only slightly for different clusters. A low-frequency band was identified that is sensitive to the conformation (trans / gauche) of the 2-phenylethanetiolate ligand.
We describe the experimental investigation of time-resolved magnetic field effects in exciplex-forming organic donor–acceptor systems. In these systems, the photoexcited acceptor state is predominantly deactivated by bimolecular electron transfer reactions (yielding radical ion pairs) or by direct exciplex formation. The delayed fluorescence emitted by the exciplex is magnetosensitive if the reaction pathway involves loose radical ion pair states. This magnetic field effect results from the coherent interconversion between the electronic singlet and triplet radical ion pair states as described by the radical pair mechanism. By monitoring the changes in the exciplex luminescence intensity when applying external magnetic fields, details of the reaction mechanism can be elucidated. In this work we present results obtained with the fluorophore-quencher pair 9,10-dimethylanthracene/N,N-dimethylaniline (DMA) in solvents of systematically varied permittivity. A simple theoretical model is introduced that allows discriminating the initial state of quenching, viz., the loose ion pair and the exciplex, based on the time-resolved magnetic field effect. The approach is validated by applying it to the isotopologous fluorophore-quencher pairs pyrene/DMA and pyrene-d10/DMA. We detect that both the exciplex and the radical ion pair are formed during the initial quenching stage. Upon increasing the solvent polarity, the relative importance of the distant electron transfer quenching increases. However, even in comparably polar media, the exciplex pathway remains remarkably significant. We discuss our results in relation to recent findings on the involvement of exciplexes in photoinduced electron transfer reactions.
The ligand exchange reaction between Au38(2-PET)24 (2-PET: 2-phenylethanethiolate) clusters and enantiopure planar chiral [2.2]paracyclophane-4-thiol 1 (PCP-4-SH) was studied using High Performance Liquid Chromatography (HPLC) and mass spectrometry. It is shown that even at the initial stage of the reaction at least three out of the four symmetry-unique sites are exchanged leading to different regioisomers of composition Au38(2-PET)23(PCP-4-S)1. Using HPLC it was possible to isolate one specific regioisomer. The latter is stable at room temperature and at slightly elevated temperatures. However, at 80° C the adsorbed thiolate (PCP-4-S) moves between different symmetry-unique sites. These observations have implications for the preparation of mixed ligand shell clusters with specific ligand patterns.
  • Molecular Dynamics Simulations of Liquid Phase Interfaces: Understanding the Structure of the Glycerol/Water–Dodecane System
    F.R. Beierlein, A.M. Krause, C.M. Jger, P. Fita, E. Vauthey and T. Clark
    Langmuir, 29 (38) , 2013, p11898-11907
    DOI:10.1021/la4021355 | unige:30152 | Abstract | Article HTML | Article PDF
Modern spectroscopic techniques such as time-resolved second-harmonic-generation spectroscopy allow molecules to be examined selectively directly at phase interfaces. Two-phase systems formed by glycerol/water and alkane layers have previously been studied by time-resolved second-harmonic-generation spectroscopic measurements. In this molecular dynamics study, a triphenylmethane dye was inserted at the glycerol/water–alkane interface and was used as a probe for local properties such as viscosity. We now show how extensive simulations over a wide range of concentrations can be used to obtain a detailed view of the molecular structure at the glycerol/water–alkane interface. Glycerol is accumulated in a double layer adjacent to the alkane interface, which results in increased viscosity of the glycerol/water phase in the direct vicinity of the interface. We also show that conformational ensembles created by classical molecular-dynamics simulations can serve as input for QM/MM calculations, yielding further information such as transition dipoles, which can be compared with spectroscopic measurements.
  • Structures and Chiroptical Properties of the BINAS-monosubstituted Au38(SCH3)24 cluster
    B. Molina, A. Snchez-Castillo, S. Knoppe, I.L Garzon, T. Brgi and A. Tlahuice-Flores
    Nanoscale, 5 (22) , 2013, p10956-10962
    DOI:10.1039/c3nr03403h | unige:31281 | Abstract | Article HTML | Article PDF
The structure and optical properties of a set of R-1,1´-binaphthyl-2,2´-dithiol (R-BINAS) monosubstituted A-Au38(SCH3)24 clusters are studied by means of time dependent density functional theory (TD-DFT). While it was proposed earlier that BINAS selectively binds to monomer motifs (SR-Au-SR) covering the Au23 core, our calculations suggest a binding mode that bridges two dimer (SR-Au-SR-Au-RS) motifs. The more stable isomers show a negligible distortion induced by BINAS adsorption on the Au38(SCH3)24 cluster which is reflected by similar optical and Circular Dichroism (CD) spectra to those found for the parent cluster. The results furthermore show that BINAS adsorption does not enhance the CD signals of the Au38(SCH3)24 cluster.
The recently reported crystal structure of the Au28(TBBT)20 cluster (TBBT: para-tert-butylbenzenethiolate) is analyzed with (Time-Dependent-) Density Functional Theory (TD-DFT). Bader charge analysis reveals a novel trimeric Au3(SR)4 binding motif. The cluster can be formulated as Au14(Au2(SR)3)4(Au3(SR)4)2. The electronic structure of the Au146+ core and the ligand-protected cluster were analyzed and their stability can be explained by formation of distorted eight-electron superatoms. Optical absorption and Circular Dichroism (CD) spectra were calculated and compared to the experiment. Assignment of handedness of the intrinsically chiral cluster is possible.
  • Experimental Evidence of Ultrafast Quenching of the 3MLCT Luminescence in Ruthenium(II) Tris-bipyridyl Complexes via a 3dd State
    Q. Sun, S. Mosquera-Vazquez, L.M. Lawson Daku, L. Gune, H.A. Goodwin, E. Vauthey and A. Hauser
    Journal of the American Chemical Society, 135 (37) , 2013, p13660-13663
    DOI:10.1021/ja407225t | unige:29641 | Abstract | Article HTML | Article PDF
Ultrafast transient absorption spectroscopy serves to identify the 3dd state as intermediate quencher state of the 3MLCT luminescence in the non-luminescent ruthenium complexes [Ru(m-bpy)3]2+ (m-bpy = 6-methyl-2,2′-bipyridine) and [Ru(tm-bpy)3]2+ (tm-bpy = 4,4′,6,6′-tetramethyl-2′,2′-bipyridine). For [Ru(m-bpy)3]2+, the population of the 3dd state from the 3MLCT state occurs within 1.6 ps, while the return to the ground state takes 450 ps. For [Ru(tm-bpy)3]2+, the corresponding values are 0.16 and 7.5 ps, respectively. According to DFT calculations, methyl groups added in the 6 and 6′ positions of bipyridine stabilize the 3dd state by ∼4000 cm–1 each, compared to [Ru(bpy)3]2+.
  • Hydrogen-fluorine exchange in NaBH4-NaBF4
    L. Rude, U. Filso, V. D'Anna, A. Spyratou Stratmann, B. Richter, S. Hino, O. Zavorotynska, M. Baricco, M.H. Srby, B.C. Hauback, H. Hagemann, F. Besenbacher, J. Skibsted and T.R. Jensen
    Physical Chemistry Chemical Physics, 15 , 2013, p18185-18194
    DOI:10.1039/c3cp52815d | unige:30153 | Abstract | Article PDF
Hydrogen-fluorine exchange in the NaBH4–NaBF4 system is investigated with a range of experimental methods combined with DFT calculations and a possible mechanism for the reactions is proposed. Fluorine substitution is observed by in-situ synchrotron radiation powder X-ray diffraction (SR-PXD) as a new Rock salt type compound with idealized composition NaBF2H2 in the temperature range T = 200 to 215 °C. Combined use of solid-state 19F MAS NMR, FT-IR and DFT calculations supports the formation of a BF2H2 complex ion, reproducing the observation of a 19F chemical shift at 144.2 ppm, which is different from that of NaBF4 at 159.2 ppm, along with the new absorption bands observed in the IR spectra. After further heating, the fluorine substituted compound becomes X-ray amorphous and decomposes to NaF at ~310 ºC. This work shows that fluorine-substituted borohydrides tend to decompose to more stable compounds, e.g. NaF, BF3 or amorphous products such as closo-boranes, e.g. Na2B12H12. The NaBH4-NaBF4 composite decomposes at lower temperatures (300 °C) compared to NaBH4 (476 °C), as observed by thermogravimetric analysis. NaBH4-NaBF4 (1:0.5) preserves 30 % of the hydrogen storage capacity after three hydrogen release and uptake cycles compared to 8 % for NaBH4 measured by the Sievert’s method under identical conditions, but more than 50 % using prolonged hydrogen absorption time. The reversible hydrogen storage capacity tends to decrease possibly due to the formation of NaF and Na2B12H12. On the other hand, the additive sodium fluoride appears to facilitate hydrogen uptake, prevent foaming, phase segregation and loss of material from the sample container for samples of NaBH4-NaF.
A major problem in the extraction of the reaction probability in bimolecular processes is the disentanglement from the influence of molecular diffusion. One of the strategies to overcome it makes use of reactive solvents in which the reactants do not need to diffuse to encounter each other. However, most of our quantitative understanding of chemical reactions in solution between free partners is based on the assumption that they can be approximated by spheres because rotation averages their mutual orientations. This condition may not be fulfilled when the reaction takes place on time scales faster than that of molecular reorientation. In this work, the fluorescence quenching of two very similar polyaromatic hydrocarbons with different electric dipole moments is measured. The concentration of a liquid electron-donating quencher is varied from very dilute solutions to pure quencher solutions. In both cases, the thermodynamics of the reactions are very similar and, according to the Marcus expression, the kinetics are expected to proceed at similar rates. However, one of them is 10 times faster in the pure quencher solution. This difference starts at relatively low quencher concentrations. An explanation based on the fluorophore–solvent dipole–dipole interaction and the consequent orientational solvent structure is provided. The orientational correlation between fluorophore and quencher is calculated by means of computer simulations. Important differences depending on the fluorophore dipole moment are found. The kinetics can be explained quantitatively with a reaction–diffusion model that incorporates the effects of the presence of the dipole moment and the rotational diffusion, only in the highest quencher concentration case, but not in dilute solutions, most likely due to fundamental limitations of the kinetic theory.
The ligand exchange reaction between monodisperse Au25(2-PET)18 (2-PET: 2-phenylethylthiolate) clusters and 1,1′-binaphthyl-2,2′-dithiol (BINAS) was long thought to induce decomposition of the cluster (Si et al., J. Phys. Chem. C, 2009). We repeated the experiment and analyzed the reaction products using MALDI-TOF mass spectrometry. The spectra clearly indicate successful ligand exchange, bidentate binding of the BINAS ligand and intact Au25 clusters. The reaction products are identified as Au25(2-PET)18−2x(BINAS)x (x = 1–4) for a 24 h reaction with a 50-fold molar excess of BINAS. Two likely binding motifs are discussed. Analysis of atomic distances in both the cluster and the free ligand indicates interstaple binding connecting the central sulfur atom of the protecting (SRAu)2SR with the outer sulfur atom of a second unit. The results presented have implications on the binding position of BINAS in Au38(SR)24−2x(BINAS)x clusters.
  • On the flexibility of the gold-thiolate interface: Racemization of the Au40(SR)24 cluster
    B. Varnholt, I. Dolamic, S. Knoppe and T. Brgi
    Nanoscale, 5 , 2013, p9568-9571
    DOI:10.1039/c3nr03389a | unige:30154 | Abstract | Article PDF
The two enantiomers of the Au40(2-PET)24 cluster were collected using HPLC and analyzed by MALDI-TOF mass spectrometry, UV-vis- and CD-spectroscopy. The flexibility of the cluster surface allows racemization of the intrinsically chiral cluster at elevated temperatures (80 – 130 °C) which was monitored following the optical activity. The determined activation energy (25 kcal/mol) lies in the range of previously reported values for Au38 nanoclusters whereas the activation entropy deviates significantly from the one in Au38. The latter may indicate that the racemization can take place via different mechanisms.
A new multiconfigurational quantum chemical method, SplitGAS, is presented. The configuration interaction expansion, generated from a generalized active space, GAS, wave function is split in two parts, a principal part containing the most relevant configurations and an extended part containing less relevant, but not negligible, configurations. The partition is based on an orbital criterion. The SplitGAS method has been employed to study the HF, N2, and Cr2 molecules. The results on these systems, especially on the challenging, multiconfigurational Cr2 molecule, are satisfactory. While SplitGAS is comparable with the GASSCF method in terms of memory requirements, it performs better than the complete active space method followed by second-order perturbation theory, CASPT2, in terms of equilibrium bond length, dissociation energy, and vibrational properties.
  • Broadband ultraviolet-visible transient absorption spectroscopy in the nanosecond to microsecond time domain with sub-nanosecond time resolution
    B. Lang, S. Mosquera-Vazquez, D. Lovy, P. Sherin, V. Markovic and E. Vauthey
    Review of Scientific Instruments, 84 (7) , 2013, p73107
    DOI:10.1063/1.4812705 | unige:28965 | Abstract | Article HTML | Article PDF
A combination of sub-nanosecond photoexcitation and femtosecond supercontinuum probing is used to extend femtosecond transient absorption spectroscopy into the nanosecond to microsecond time domain. Employing a passively Q-switched frequency tripled Nd:YAG laser and determining the jitter of the time delay between excitation and probe pulses with a high resolution time delay counter on a single-shot basis leads to a time resolution of 350 ps in picosecond excitation mode. The time overlap of almost an order of magnitude between fs and sub-ns excitation mode permits to extend ultrafast transient absorption (TA) experiments seamlessly into time ranges traditionally covered by laser flash photolysis. The broadband detection scheme eases the identification of intermediate reaction products which may remain undetected in single-wavelength detection flash photolysis arrangements. Single-shot referencing of the supercontinuum probe with two identical spectrometer/CCD arrangements yields an excellent signal-to-noise ratio for the so far investigated chromophores in short to moderate accumulation times.
  • Complexes with Redox-Active Ligands: Synthesis, Structure, and Electrochemical and Photophysical Behavior of the Ru(II) Complex with TTF-Annulated Phenanthroline
    L.K. Keniley, N. Dupont, L. Ray, J. Ding, K. Kovnir, J.M. Hoyt, A. Hauser and M. Shatruk
    Inorganic Chemistry, 52 (14) , 2013, p8040-8052
    DOI:10.1021/ic4006949 | unige:28963 | Abstract | Article HTML | Article PDF
Ru(II) complexes with chelating ligands, 4′,5′-ethylenedithiotetrathiafulvenyl[4,5-f][1,10]phenanthroline (L1), 1,3-dithiole-2-thiono[4,5-f][1,10]phenanthroline (L2), and 1,3-dithiole-2-ono[4,5-f][1,10]phenanthroline (L3), have been prepared and their structural, electrochemical, and photophysical properties investigated. Density functional theory (DFT) calculations indicate that the highest occupied molecular orbital of [Ru(bpy)2(L1)](PF6)2 (1) is located on the tetrathiafulvalene (TTF) subunit and appears ≈0.6 eV above the three Ru-centered d orbitals. In agreement with this finding, 1 exhibits three reversible oxidations: the two at lower potentials take place on the TTF subunit, and the one at higher potential is due to the Ru3+/Ru2+ redox couple. Complexes [Ru(bpy)2(L2)](PF6)2 (2) and [Ru(bpy)2(L3)](PF6)2 (3) exhibit only the Ru3+/Ru2+-related oxidation. The optical absorption spectra of all complexes reveal a characteristic metal-to-ligand charge transfer (MLCT) band centered around 450 nm. In addition, in the spectrum of 1 the MLCT band is augmented by a low-energy tail that extends beyond 500 nm and is attributed to the intraligand charge transfer (ILCT) transition of L1, according to time-dependent DFT calculations. The substantial decrease in the luminescence quantum yield of 1 compared to those of 2 and 3 is attributed to the reductive quenching of the emissive state via electron transfer from the TTF subunit to the Ru3+ center, thus allowing nonradiative relaxation to the ground state through the lower-lying ILCT state. In the presence of O2, complex 1 undergoes a photoinduced oxidative cleavage of the central C═C bond of the TTF fragment, resulting in complete transformation to 3. This photodegradation process was studied with 13C NMR and optical absorption spectroscopy.
  • Light Induced Bistability in the 2D Coordination Network {[Fe(bbtr)3](BF4)2}: Wavelength-Selective Addressing of Molecular Spin States
    P. Chakraborty, S. Pillet, E.-E. Bendeif, C. Enachescu, R. Bronisz and A. Hauser
    Chemistry - A European Journal, 19 (34) , 2013, p11418-11428
    DOI:10.1002/chem.201301257 | unige:29524 | Abstract | Article PDF
Whereas the neat polymeric Fe(II) compound {[Fe(bbtr)3](ClO4)2} (bbtr=1,4-di(1,2,3-triazol-1-yl)butane) shows an abrupt spin transition centered at 107 K facilitated by a crystallographic symmetry breaking, in the covalently linked 2D coordination network of {[Fe(bbtr)3](BF4)2}, Fe(II) stays in the high-spin state down to 10 K. However, strong cooperative effects of elastic origin result in reversible, persistent and wavelength-selective photoswitching between the low-spin and high-spin manifolds. This compound thus shows true light-induced bistability below 100 K. The persistent bidirectional optical switching behavior is discussed as a function of temperature, irradiation time and intensity. Crystallographic studies reveal a photo-induced symmetry breaking and serve to establish the correlation between structure and cooperative effects. The static and kinetic behavior is explicated within the framework of the mean-field approximation.
  • Stabilization of Thiolate-Protected Gold Clusters against Thermal Inversion: Diastereomeric Au38(SCH2CH2Ph)24-2x(R-BINAS)x
    S. Knoppe, S. Michalet and T. Brgi
    Journal of Physical Chemistry C, 117 (29) , 2013, p15354-15361
    DOI:10.1021/jp4040908 | unige:29224 | Abstract | Article PDF
Intrinsically chiral thiolate-protected gold clusters were recently separated into their enantiomers and their circular dichroism (CD) spectra were measured. Introduction of the chiral R-1,1’-binaphthyl-2,2’-dithiol (BINAS) into the ligand layer of rac-Au38(2-PET)24 clusters (2-PET: 2-phenylethylthiolate, SCH2CH2Ph) was shown to be diastereoselective. In this contribution, we isolated and characterized the diastereomeric reaction products of the first exchange step, A-Au38(2-PET)22(R-BINAS)1 and C-Au38(2-PET)22(R-BINAS)1 (A/C, anti-clockwise/clockwise) and the second exchange product, A-Au38(2-PET)20(R-BINAS)2. The absorption spectra show minor, but significant influence of the BINAS ligand. Overall, the spectra are less defined compared to Au38(2-PET)24, which is ascribed to symmetry breaking. The CD spectra are similar to those of the parent Au38(2-PET)24 enantiomers, readily allowing the assignment of handedness of the ligand layer. Nevertheless, some characteristic differences are found between the diastereomers. The anisotropy factors are slightly lower after ligand exchange. The second exchange step seems to confirm the trend. Inversion experiments were performed and compared to the racemization of Au38(2-PET)24. It was found that the introduction of the BINAS ligand effectively stabilizes the cluster against inversion, which involves a rearrangement of the thiolates on the cluster surface. It therefore seems that introduction of the di-thiol reduces the flexibility of the gold-sulfur interface.
  • Determination of the molecular structure of the short-lived light-induced high-spin state in the spin-crossover compound [Fe(6-mepy)3tren](PF6)2
    P. Chakraborty, A. Tissot, L. Peterhans, L. Gune, C. Besnard, P. Pattison and A. Hauser
    Physical Review B, 87 (21) , 2013, p214306
    DOI:10.1103/PhysRevB.87.214306 | unige:28964 | Abstract | Article PDF
In the spin-crossover compound [Fe(6-mepy)3tren](PF6)2, (6-mepy)3tren = tris{4-[(6-methyl)-2-pyridyl]-3-aza-butenyl}amine, the high-spin state can be populated as metastable state below the thermal transition temperature via irradiation into the metal to ligand charge transfer absorption band of the low-spin species. At 10 K, the lifetime of this metastable state is only 1 s. Despite this, it is possible to determine an accurate excited state structure by following the evolution of relevant structural parameters by synchrotron X-ray diffraction under continuous irradiation with increasing intensity. The difference in metal-ligand bond length between the high-spin and the low-spin state is found to be 0.192 Å obtained from an analysis of the experimental data using the mean-field approximation to model cooperative effects.
  • Real-Time Observation of the Formation of Excited Radical Ions in Bimolecular Photoinduced Charge Separation: Absence of the Marcus Inverted Region Explained
    M. Koch, A. Rosspeintner, K. Adamczyk, B. Lang, J. Dreyer, E.T.J. Nibbering and E. Vauthey
    Journal of the American Chemical Society, 135 (26) , 2013, p9843-9848
    DOI:10.1021/ja403481v | unige:28966 | Abstract | Article HTML | Article PDF
Unambiguous evidence for the formation of excited ions upon ultrafast bimolecular photoinduced charge separation is found using a combination of femtosecond time-resolved fluorescence up-conversion, infrared and visible transient absorption spectroscopy. The reaction pathways are tracked by monitoring the vibrational energy redistribution in the product after charge separation and subsequent charge recombination. For moderately exergonic reactions, both donor and acceptor are found to be vibrationally hot, pointing to an even redistribution of the energy dissipated upon charge separation and recombination in both reaction partners. For highly exergonic reactions, the donor is very hot, whereas the acceptor is mostly cold. The asymmetric energy redistribution is due to the formation of the donor cation in an electronic excited state upon charge separation, confirming one of the hypotheses for the absence of the Marcus inverted region in photoinduced bimolecular charge separation processes
  • A modified cyclen azaxanthone ligand as a new fluorescent probe for Zn2+
    H. Nouri, C. Cadiou, L.M. Lawson Daku, A. Hauser, S. Chevreux, I. Dchamps-Olivier, F. Lachaud, R. Ternane, M. Trabelsi-Ayadi, F. Chuburu and G. Lemercier
    Dalton Transactions, 42 , 2013, p12157-12164
    DOI:10.1039/c3dt51216a | unige:29225 | Abstract | Article PDF
A new cyclen derivative L, bearing a methyl-chromeno-pyridinylidene hydrazone moiety, was synthesized and studied in MeOH, as potential fluorescent “OFF-on-ON” sensors for Zn(II). Photocphysical properties of this ligand being PET regulated, L was only weakly emissive in the absence of metal ions (OFF). L fluorescence was increased modestly upon addition of one equivalent of Zn(II), and further increased upon addition of a second equivalent. Therefore, Zn:L behaved as a highly sensitive ON sensor for zinc. This efficiency was correlated to Zn(II) coordination via the hydrazone moiety of the fluorophore, producing an efficient CHelation-Enhanced Fluorescence (CHEF) effect. A complementary theoretical study carried out with DFT calculations further elucidated of the optical properties.
A switch in time: A fast precipitation technique was used to prepare 75 nm FeII spin-crossover nanocrystals. Their photoswitching dynamics, based on the light-induced excited spin-state trapping effect, has been investigated by means of optical spectroscopy. A significant variation of the switching proprieties is observed compared to similar but amorphous nanoparticles.
  • Stimuli Responsive Hybrid Magnets: Tuning the Photoinduced Spin-Crossover in Fe(III) Complexes Inserted into Layered Magnets
    M. Clemente-Len, E. Coronado, M. Lpez-Jord, J.C. Waerenborgh, C. Desplanches, H. Wang, J.-F. Ltard, A. Hauser and A. Tissot
    Journal of the American Chemical Society, 135 (23) , 2013, p8655-8667
    DOI:10.1021/ja402674x | unige:28703 | Abstract | Article HTML | Article PDF
The insertion of a [Fe(sal2-trien)]+ complex cation into a 2D oxalate network in the presence of different solvents results in a family of hybrid magnets with coexistence of magnetic ordering and photoinduced spin-crossover (LIESST effect) in compounds [FeIII(sal2-trien)][MnIICrIII(ox)3]·CHCl3 (1·CHCl3), [FeIII(sal2-trien)][MnIICrIII(ox)3]·CHBr3 (1·CHBr3), and [FeIII(sal2-trien)][MnIICrIII(ox)3]·CH2Br2 (1·CH2Br2). The three compounds crystallize in a 2D honeycomb anionic layer formed by MnII and CrIII ions linked through oxalate ligands and a layer of [Fe(sal2-trien)]+ complexes and solvent molecules (CHCl3, CHBr3, or CH2Br2) intercalated between the 2D oxalate network. The magnetic properties and Mössbauer spectroscopy indicate that they undergo long-range ferromagnetic ordering at 5.6 K and a spin crossover of the intercalated [Fe(sal2-trien)]+ complexes at different temperatures T1/2. The three compounds present a LIESST effect with a relaxation temperature TLIESST inversely proportional to T1/2. The isostructural paramagnetic compound, [FeIII(sal2-trien)][ZnIICrIII(ox)3]·CH2Cl2 (2·CH2Cl2) was also prepared. This compound presents a partial spin crossover of the inserted FeIII complex as well as a LIESST effect. Finally, spectroscopic characterization of the FeIII doped compound [Ga0.99Fe0.01(sal2trien)][MnIICrIII(ox)3]·CH2Cl2 (3·CH2Cl2) shows a gradual and complete thermal spin crossover and a LIESST effect on the isolated FeIII complexes. This result confirms that cooperativity is not a necessary condition to observe the LIESST effect in an FeIII compound.
  • Extracting Information about Chemical Bonding from Molecular Electron Densities via Single Exponential Decay Detector (SEDD)
    P. De Silva, J. Korchowiec, N.J.S. Ram and T.A. Wesolowski
    Chimia, 67 (4) , 2013, p253-256
    DOI:10.2533/chimia.2013.253 | unige:28399 | Abstract | Article PDF
The recently introduced molecular descriptor (Single Exponential Decay Detector - SEDD) [P. de Silva, J. Korchowiec, T. A. Wesolowski, ChemPhysChem 201213, 3462] is used to visualize bonding patterns in molecules. In each point of space SEDD is simply related to the electron density:

SEDD(r) = ln[1/ρ2(∇(∇ρ/ρ)2)2}.

Either experimental or computed densities ρ(r) can be used to evaluate SEDD. Here, maps of SEDD are obtained from theoretical densities and reveal such features as core electrons, chemical bonds, lone pairs and delocalization in aromatic systems. It is shown that SEDD provides fingerprints of aromaticity, which can be separated into geometric and electronic effects.

  • Non-additive kinetic energy and potential in analytically solvable systems and their approximated counterparts
    T.A. Wesolowski and A. Savin
    in "Recent Progress in Orbital-free Density Functional Theory (Recent Advances in Computational Chemistry Vol. 6)" T.A. Wesolowski and Y.A. Wang Eds., World Scientific, 6 , 2013, p275-295
    DOI:10.1142/9789814436731_0009 | unige:28400 | Abstract | Article PDF
The one-electron equation for orbitals embedded in frozen electron density (Eqs. 20-21 in [Wesolowski and Warshel, J. Phys. Chem, 97 (1993) 8050]) in its exact and approximated version is solved for an analytically solvable model system. The system is used to discuss the role of the embedding potential in preventing the collapse of a variationally obtained electron density onto the nucleus in the case when the frozen density is chosen to be that of the innermost shell. The approximated potential obtained from the second-order gradient expansion for the kinetic energy prevents such a collapse almost perfectly but this results from partial compensation of flaws of its components. It is also shown that that the quality of a semi-local approximation to the kinetic-energy functional, a quantity needed in orbital-free methods, is not related to the quality of the non-additive kinetic energy potential - a key component of the effective embedding potential in one-electron equations for embedded orbitals.
  • Semilocal approximations for the kinetic energy
    F. Tran and T.A. Wesolowski
    in "Recent Progress in Orbital-free Density Functional Theory (Recent Advances in Computational Chemistry Vol. 6)" T.A. Wesolowski and Y.A. Wang Eds., World Scientific, 6 , 2013, p429-442
    DOI:10.1142/9789814436731_0016 | unige:28401 | Abstract | Article PDF
Approximations to the non-interacting kinetic energy Ts[ρ], which take the form of semilocal analytic expressions are collected. They are grouped according to the quantities on which they explicitly depend. Additionally, the approximations for quantities related to Ts[ρ] (kinetic potential and non-additive kinetic energy), for which the analytic expressions for the “parent” approximation for the functional Ts[ρ] are unknown, are also given.
Four-dimensional (4D) electron microscopy (EM) uniquely combines the high spatial resolution to pinpoint individual nano-objects, with the high temporal resolution necessary to address the dynamics of their laser-induced transformation. Here, using 4D-EM, we demonstrate the in situ irreversible transformation of individual nanoparticles of the molecular framework Fe(pyrazine)Pt(CN)4. The newly formed material exhibits an unusually large negative thermal expansion (i.e. contraction), which is revealed by time-resolved imaging and diffraction. Negative thermal expansion is a unique property exhibited by only few materials. Here we show that the increased flexibility of the metal–cyanide framework after the removal of the bridging pyrazine ligands is responsible for the negative thermal expansion behavior of the new material. This in situ visualization of single nanostructures during reactions should be extendable to other classes of reactive systems.
  • Chiroptical Properties of Intrinsically Chiral Thiolate-protected Gold Clusters
    S. Knoppe and T. Brgi
    Chimia, 67 (4) , 2013, p236-239
    DOI:10.2533/chimia.2013.236 | unige:27716 | Abstract | Article PDF
Chiral thiolate-protected gold clusters of atomic precision have gained increasing interest in recent years due to their potential use in catalysis, sensing or bioapplications. While the protection of gold clusters with chiral ligands is a rather trivial task, it was found that the clusters can bear intrinsically chiral features, most obvious in the arrangement of the protecting ligands on the surface of the cluster. Recent efforts showed the separation of the enantiomers of such intrinsically chiral gold clusters. This technique can be used for the prediction of chirality in structurally unknown clusters. Activation barriers for the racemization of Au38(SR)24 were determined. As this involves a huge rearrangement of the ligands, the flexibility of the gold-thiolate interface is demonstrated. Furthermore, the ligand exchange reactions between intrinsically chiral clusters and bidentate chiral thiols were studied. A limited, regioselective exchange was found. Most importantly, the reaction is diastereoselective and allows tailoring of gold clusters that are protected with a defined layer of ligands.
  • Single-nanoparticle phase transitions visualized by four-dimensional electron microscopy
    R.M. Van der Veen, O.-H. Kwon, A. Tissot, A. Hauser and A.H. Zewail
    Nature Chemistry, 5 (5) , 2013, p395-402
    DOI:10.1038/NCHEM.1622 | unige:27715 | Abstract | Article HTML | Article PDF

The advancement of techniques that can probe the behaviour of individual nanoscopic objects is of paramount importance in various disciplines, including photonics and electronics. As it provides images with a spatiotemporal resolution, four-dimensional electron microscopy, in principle, should enable the visualization of single-nanoparticle structural dynamics in real and reciprocal space. Here, we demonstrate the selectivity and sensitivity of the technique by visualizing the spin crossover dynamics of single, isolated metal–organic framework nanocrystals. By introducing a small aperture in the microscope, it was possible to follow the phase transition and the associated structural dynamics within a single particle. Its behaviour was observed to be distinct from that imaged by averaging over ensembles of heterogeneous nanoparticles. The approach reported here has potential applications in other nanosystems and those that undergo (bio)chemical transformations.
The crystal structures of the M2NaIO6 series (M = Ca, Sr, Ba), prepared at 650 °C by ceramic methods, were determined from conventional laboratory X-ray powder diffraction data. Synthesis and crystal growth were made by oxidizing I with O2(air) to I7+ followed by crystal growth in the presence of NaF as mineralizator, or by the reaction of the alkali-metal periodate with the alkaline-earth metal hydroxide. All three compounds are insoluble and stable in water. The barium compound crystallizes in the cubic space group Fm3m (no. 225) with lattice parameters of a = 8.3384(1) Å, whereas the strontium and calcium compounds crystallize in the monoclinic space group P21/c (no. 14) with a = 5.7600(1) Å, b = 5.7759(1) Å, c = 9.9742(1) Å, β = 125.362(1)° and a = 5.5376(1) Å, b = 5.7911(1) Å, c = 9.6055(1) Å, β = 124.300(1)°, respectively. The crystal structure consists of either symmetric (for Ba) or distorted (for Sr and Ca) perovskite superstructures. Ba2NaIO6 contains the first perfectly octahedral [IO6]5– unit reported. The compounds of the ortho-periodates are stable up to 800 °C. Spectroscopic measurements as well as DFT calculations show a reasonable agreement between calculated and observed IR- and Raman-active vibrations.
  • Tetrathiafulvalene-1,3,5-triazines as (Multi)Donor-Acceptor Systems with Tunable Charge Transfer: Structural, Photophysical, and Theoretical Investigations
    F. Pop, F. Riob, S. Seifert, T. Cauchy, J. Ding, N. Dupont, A. Hauser, M. Koch and N. Avarvari
    Inorganic Chemistry, 52 (9) , 2013, p5023-5034
    DOI:10.1021/ic3027336 | unige:27865 | Abstract | Article HTML | Article PDF
Palladium-catalyzed cross-coupling reactions between chlorinated 1,3,5-triazines (TZ) and tetrathiafulvalene (TTF) trimethyltin derivatives afford mono- and C3 symmetric tris(TTF)-triazines as donor–acceptor compounds in which the intramolecular charge transfer (ICT) is modulated by the substitution scheme on TTF and TZ and by chemical or electrochemical oxidation. The TTF-TZ-Cl2 and (SMe)2TTF-TZ-Cl2 derivatives show fully planar structures in the solid state as a consequence of the conjugation between the two units. Electrochemical and photophysical investigations, supported by theoretical calculations, clearly demonstrate that the lowest excited state can be ascribed to the intramolecular charge transfer (ICT) π(TTF)→π*(TZ) transition. The tris(TTF) compound [(SMe)2TTF]3-TZ shows fluorescence when excited in the ICT band, and the emission is quenched upon oxidation. The radical cations TTF+• are easily observed in all of the cases through chemical and electrochemical oxidation by steady-state absorption experiments. In the case of [(SMe)2TTF]3-TZ, a low energy band at 5000 cm–1, corresponding to a coupling between TTF+• and TTF units, is observed. A crystalline radical cation salt with the TTF-TZ-Cl2 donor and PF6 anion, prepared by electrocrystallization, is described.
Ultrafast photochemical processes can occur in parallel with the relaxation of the optically populated excited state toward equilibrium. The latter involves both intra- and intermolecular modes, namely vibrational and solvent coordinates, and takes place on timescales ranging from a few tens of femtoseconds to up to hundreds of picoseconds, depending on the system. As a consequence, the reaction dynamics can substantially differ from those usually measured with slower photoinduced processes occurring from equil-ibrated excited states. For example, the decay of the excited-state population may become strongly nonexponential and depend on the excitation wavelength, contrary to the Kasha and Vavilov rules. In this article, we first give a brief account of our current understanding of vibrational and solvent relaxation processes. We then present an overview of important classes of ultrafast photochemical reactions, namely electron and proton transfer as well as isomerization, and illustrate with several examples how nonequilibrium effects can affect their dynamics.
  • Chiral Selectivity in the Binding of [4]Helicene Derivatives to Double-Stranded DNA
    O. Kel, A. Frstenberg, N. Mehanna, C. Nicolas, B. Laleu, M. Hammarson, B. Albinsson, J. Lacour and E. Vauthey
    Chemistry - A European Journal, 19 (22) , 2013, p7173-7180
    DOI:10.1002/chem.201203915 | unige:27926 | Abstract | Article HTML | Article PDF
The interaction of a series of chiral cationic [4]helicene derivatives, which differ by their substituents, with double-stranded DNA has been investigated by using a combination of spectroscopic techniques, including time-resolved fluorescence, fluorescence anisotropy, and linear dichroism. Addition of DNA to helicene solutions results to a hypochromic shift of the visible absorption bands, an increase of fluorescence quantum yield and lifetime, a slowing down of fluorescence anisotropy decay, and a linear dichroism in flow-oriented DNA, which unambiguously points to the binding of these dyes to DNA. Both helicene monomers and dimeric aggregates, which form at higher concentration, bind to DNA, the former most probably upon intercalation and the latter upon groove binding. The binding constant depends substantially on the dye substituents and is, in all cases, larger with the M than the P enantiomer, by factors ranging from 1.2 to 2.3, depending on the dye.