TY - JOUR
AU - Sissaoui, J.
AU - Budkina, D.S.
AU - Vauthey, E.
TI - Probing Liquid Interfaces with Room-Temperature Ionic Liquids Using the Excited-State Dynamics of a Cationic Dye
PY - 2020
JF - Journal of Physical Chemistry B
JA - J. Phys. Chem. B
SN - 1520-6106
VL - 124
SP - 10546
EP - 10555
L1 - https://pubs.acs.org/doi/pdf/10.1021/acs.jpcb.0c07803
L2 - https://pubs.acs.org/doi/10.1021/acs.jpcb.0c07803
L3 - https://pubs.acs.org/doi/10.1021/acs.jpcb.0c07803
L4 - http://www.unige.ch/sciences/chifi/publis/pics/double/ref01657.png
M3 - 10.1021/acs.jpcb.0c07803
UR - http://dx.doi.org/10.1021/acs.jpcb.0c07803
N2 - Interfaces with room-temperature ionic liquids (ILs) play key roles in many applications of these solvents, but our understanding of their properties is still limited. We investigate how the addition of ILs in the aqueous subphase affects the adsorption of the cationic dye malachite green at the dodecane/water interface using stationary and time-resolved surface second harmonic generation. We find that the interfacial concentration of malachite green depends crucially on the nature of both anionic and cationic constituents. This concentration reports on the overall charge of the interface, which itself depends on the relative interfacial affinity of the ions. Our results reveal that the addition of ILs to the aqueous subphase has similar effects to the addition of conventional salts. However, the IL cations have a significantly higher propensity to adsorb than small inorganic cations. Furthermore, the IL constituents show a synergistic effect, as the interfacial concentration of each of them also depends on the interfacial affinity of the other.
ID - 1657
ER -
TY - JOUR
AU - Dereka, B.
AU - Rosspeintner, A.
AU - Svechkarev, D.
AU - Vauthey, E.
TI - Comment on “Theoretical Insights into the Excited State Decays of a Donor–Acceptor Dyad: Is the Twisted and Rehybridized Intramolecular Charge-Transfer State Involved?”
PY - 2020
JF - Journal of Physical Chemistry B
JA - J. Phys. Chem. B
SN - 1520-6106
VL - 124
SP - 10578
EP - 10581
L1 - https://pubs.acs.org/doi/pdf/10.1021/acs.jpcb.0c06526
L2 - https://pubs.acs.org/doi/10.1021/acs.jpcb.0c06526
L3 - https://pubs.acs.org/doi/10.1021/acs.jpcb.0c06526
M3 - 10.1021/acs.jpcb.0c06526
UR - http://dx.doi.org/10.1021/acs.jpcb.0c06526
ID - 1656
ER -
TY - JOUR
AU - Shybeka, I.
AU - Aster, A.
AU - Cheng, Y.
AU - Sakai, N.
AU - Frontera, A.
AU - Vauthey, E.
AU - Matile, S.
TI - Naphthalenediimides with Cyclic Oligochalcogenides in Their Core
PY - 2020
JF - Chemistry - A European Journal
JA - Chem. - Eur. J.
SN - 0947-6539
VL - 26
SP - 14059
EP - 14063
L1 - https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/chem.202003550
L2 - https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/chem.202003550
L3 - https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/chem.202003550
L4 - http://www.unige.ch/sciences/chifi/publis/pics/double/ref01655.png
M3 - 10.1002/chem.202003550
UR - http://dx.doi.org/10.1002/chem.202003550
N2 - Naphthalenediimides (NDIs) are privileged scaffolds par excellence, of use in functional systems from catalysts to ion channels, photosystems, sensors, ordered matter in all forms, tubes, knots, stacks, sheets, vesicles, and colored over the full visible range. Despite this extensively explored chemical space, there is still room to discover core-substituted NDIs with fundamentally new properties: NDIs with cyclic trisulfides (i.e., trisulfanes) in their core absåorb at 668?nm, emit at 801?nm, and contract into disulfides (i.e., dithietes) upon irradiation at
ID - 1655
ER -
TY - JOUR
AU - Rumble, C.
AU - Licari, G.
AU - Vauthey, E.
TI - Molecular Dynamics Simulations of Bimolecular Electron Transfer: Testing the Coulomb Term in the Weller Equation
PY - 2020
JF - Journal of Physical Chemistry B
JA - J. Phys. Chem. B
SN - 1520-6106
VL - 124
SP - 9945
EP - 9950
L1 - https://pubs.acs.org/doi/pdf/10.1021/acs.jpcb.0c09031
L2 - https://pubs.acs.org/doi/10.1021/acs.jpcb.0c09031
L3 - https://pubs.acs.org/doi/10.1021/acs.jpcb.0c09031
L4 - http://www.unige.ch/sciences/chifi/publis/pics/double/ref01654.png
M3 - 10.1021/acs.jpcb.0c09031
UR - http://dx.doi.org/10.1021/acs.jpcb.0c09031
N2 - Reliable estimation of the driving force for photoinduced electron transfer between neutral reactants is of utmost importance for most practical applications of these reactions. The driving force is usually calculated from the Weller equation, which contains a Coulomb term, C, whose magnitude in polar solvents is debated. We have performed umbrella sampling molecular dynamics simulations to determine C from the potentials of mean force between neutral and ionic donor/acceptor pairs of different sizes in solvents of varying polarity. According to the simulations, C in polar solvents is a factor of 2 more negative than typically calculated according to the Weller equation. Use of the À-stack contact distance in the Weller equation instead of the van der Waals radius recovers the correct value of C, but this is mostly fortuitous due to the compensating effects of overestimating the dielectric screening at contact and neglecting both charge dilution and desolvation.
ID - 1654
ER -
TY - JOUR
AU - Szakacs, Z.
AU - Tasior, M.
AU - Gryko, D.
AU - Vauthey,
TI - Change of Quadrupole Moment upon Excitation and Symmetry Breaking in Multibranched Donor-Acceptor Dyes
PY - 2020
JF - ChemPhysChem
JA - ChemPhysChem
SN - 1439-4235
VL - 21
SP - 1718
EP - 1730
L1 - https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/cphc.202000253
L2 - https://chemistry-europe.onlinelibrary.wiley.com/doi/full/10.1002/cphc.202000253
L3 - https://chemistry-europe.onlinelibrary.wiley.com/doi/full/10.1002/cphc.202000253
L4 - http://www.unige.ch/sciences/chifi/publis/pics/double/ref01653.png
M3 - 10.1002/cphc.202000253
UR - http://dx.doi.org/10.1002/cphc.202000253
ID - 1653
ER -
TY - JOUR
AU - Verma, P.
AU - Rosspeintner, A.
AU - Dereka, B.
AU - Vauthey, E.
AU - Kumpulainen, T.
TI - Broadband Fluorescence Reveals Mechanistic Differences in Excited-State Proton Transfer to Protic and Aprotic Solvents
PY - 2020
JF - Chemical Science
JA - Chem. Sci.
SN - 2041-6520
VL - 11
SP - 7963
EP - 7971
L1 - https://pubs.rsc.org/en/content/articlepdf/2020/sc/d0sc03316b
L2 - https://pubs.rsc.org/en/content/articlehtml/2020/sc/d0sc03316b
L3 - https://pubs.rsc.org/en/content/articlelanding/2020/SC/D0SC03316B#!divAbstract
M3 - 10.1039/D0SC03316B
UR - http://dx.doi.org/10.1039/D0SC03316B
ID - 1652
ER -
TY - JOUR
AU - Garca-Calvo, J.
AU - Maillard, J.
AU - Fureraj, I.
AU - Strakova, K.
AU - Colom, A.
AU - Mercier, V.
AU - Roux, A.
AU - Vauthey, E.
AU - Sakai, N.
AU - Frstenberg, A.
AU - Matile, S
TI - Fluorescent Membrane Tension Probes for Super-Resolution Microscopy: Combining Mechanosensitive Cascade Switching with Dynamic-Covalent Ketone Chemistry
PY - 2020
JF - Journal of the American Chemical Society
JA - J. Am. Chem. Soc.
SN - 0002-7863
VL - 142
SP - 12034
EP - 12038
L1 - https://pubs.acs.org/doi/pdf/10.1021/jacs.0c04942
L2 - https://pubs.acs.org/doi/10.1021/jacs.0c04942
L3 - https://pubs.acs.org/doi/10.1021/jacs.0c04942
M3 - 10.1021/jacs.0c04942
UR - http://dx.doi.org/10.1021/jacs.0c04942
ID - 1651
ER -
TY - JOUR
AU - Nanoz, C.
AU - Rumble, C.
AU - Rosspeintner, A.
AU - Vauthey, E
TI - Bimolecular photoinduced electron transfer in non-polar solvents beyond the diffusion limit
PY - 2020
JF - Journal of Chemical Physics
JA - J. Chem. Phys.
SN - 0021-9606
VL - 152
SP - 244501
L1 - https://aip.scitation.org/doi/pdf/10.1063/5.0012363
L2 - https://aip.scitation.org/doi/full/10.1063/5.0012363
L3 - https://aip.scitation.org/doi/full/10.1063/5.0012363
L4 - http://www.unige.ch/sciences/chifi/publis/pics/double/ref01650.png
M3 - 10.1063/5.0012363
UR - http://dx.doi.org/10.1063/5.0012363
ID - 1650
ER -
TY - JOUR
AU - Bentounsi, Y.
AU - Seintis, K.
AU - Ameline, D.
AU - Diring, S.
AU - Provost, D.
AU - Blart, E.
AU - Pellegrin, Y.
AU - Cossement, D.
AU - Vauthey, E.
AU - Odobel, F
TI - Chemistry on the electrodes: post-functionalization and stability enhancement of anchored dyes on mesoporous metal oxide photoelectrochemical cells with copper-free Huisgen cycloaddition reaction
PY - 2020
JF - J. Mater. Chem. A
JA - J. Mater. Chem. A
VL - 8
SP - 12633
EP - 12640
L1 - https://pubs.rsc.org/en/content/articlepdf/2020/ta/d0ta04982d
L2 - https://pubs.rsc.org/en/content/articlelanding/2020/TA/D0TA04982D#!divAbstract
L3 - https://pubs.rsc.org/en/content/articlelanding/2020/TA/D0TA04982D#!divAbstract
L4 - http://www.unige.ch/sciences/chifi/publis/pics/double/ref01649.png
M3 - 10.1039/D0TA04982D
UR - http://dx.doi.org/10.1039/D0TA04982D
ID - 1649
ER -
TY - JOUR
AU - Humeniuk, H.V.
AU - Licari, G.
AU - Vauthey, E.
AU - Sakai, N.
AU - Matile, S.
TI - Mechanosensitive membrane probes: push-pull papillons
PY - 2020
JF - Supramol. Chem.
JA - Supramol. Chem.
VL - 32
SP - 106
EP - 111
L1 - https://www.tandfonline.com/doi/pdf/10.1080/10610278.2019.1702193?needAccess=true
L2 - https://www.tandfonline.com/doi/full/10.1080/10610278.2019.1702193
L3 - https://www.tandfonline.com/doi/full/10.1080/10610278.2019.1702193
M3 - 10.1080/10610278.2019.1702193
UR - http://dx.doi.org/10.1080/10610278.2019.1702193
N2 - Design, synthesis and evaluation of push-pull N,N′-diphenyl-dihydrodibenzo[a,c]phenazines are reported. Consistent with theoretical predictions, donors and acceptors attached to the bent mechanophore are shown to shift absorption maxima to either red or blue, depending on their positioning in the chromophore. Redshifted excitation of push-pull fluorophores is reflected in redshifted emission of both bent and planar excited states. The intensity ratios of the dual emission in more and less polar solvents imply that excited-state (ES) planarization decelerates with increasing fluorophore macrodipole, presumably due to attraction between the wings of closed papillons. ES planarization of highly polarisable papillons is not observed in lipid bilayer membranes. All push-pull papillon amphiphiles excel with aggregation-induced emission (AIE) from bent ES as micelles in water and mechanosensitivity in viscous solvents. They are not solvatochromic and only weakly fluorescent (QY < 4%).
ID - 1648
ER -
TY - JOUR
AU - Beckwith, J.S.
AU - Rumble, C.A.
AU - Vauthey, E.
TI - Data analysis in transient electronic spectroscopy: an experimentalist's view
PY - 2020
JF - International Reviews in Physical Chemistry
JA - Intl. Rev. Phys. Chem.
SN - 0144-235X
VL - 39
IS - 2
SP - 213
EP - 216
L1 - https://www.tandfonline.com/doi/pdf/10.1080/0144235X.2020.1757942?needAccess=true
L2 - https://www.tandfonline.com/doi/full/10.1080/0144235X.2020.1757942
L3 - https://www.tandfonline.com/doi/full/10.1080/0144235X.2020.1757942
L4 - http://www.unige.ch/sciences/chifi/publis/pics/double/ref01647.png
M3 - 10.1080/0144235X.2020.1757942
UR - http://dx.doi.org/10.1080/0144235X.2020.1757942
ID - 1647
ER -
TY - JOUR
AU - Dereka, B.
AU - Svechkarev, D.
AU - Rosspeintner, A.
AU - Aster, A.
AU - Lunzer, M.
AU - Liska, R.
AU - Mohs, A.M.
AU - Vauthey, E.
TI - Solvent tuning of photochemistry upon excited-state symmetry breaking
PY - 2020
JF - Nature Communications
JA - Nature Comm.
SN - 2041-1723
VL - 11
IS - 1
SP - 1925
L1 - https://www.nature.com/articles/s41467-020-15681-3.pdf
L2 - https://www.nature.com/articles/s41467-020-15681-3
L3 - https://www.nature.com/articles/s41467-020-15681-3
L4 - http://www.unige.ch/sciences/chifi/publis/pics/double/ref01646.png
M3 - 10.1038/s41467-020-15681-3
UR - http://dx.doi.org/10.1038/s41467-020-15681-3
N2 - 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(-Ï€-D)2,3 molecules with photoisomerizable A-Ï€-D branches. Excited-state symmetry breaking is identified by monitoring several spectroscopic signatures of the multipolar delocalized exciton, including the S2â†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.
ID - 1646
ER -
TY - JOUR
AU - Nazarov, A.E.
AU - Ivanov, A.I.
AU - Vauthey, E.
TI - Modelling IR Spectral Dynamics upon Symmetry Breaking of a Photo-Excited Quadrupolar Dye
PY - 2020
JF - Journal of Physical Chemistry C
JA - J. Phys. Chem. C
SN - 1932-7447
VL - 124
SP - 2357
EP - 2369
L1 - https://pubs.acs.org/doi/pdf/10.1021/acs.jpcc.9b10565
L2 - https://pubs.acs.org/doi/10.1021/acs.jpcc.9b10565
L3 - https://pubs.acs.org/doi/10.1021/acs.jpcc.9b10565
L4 - http://www.unige.ch/sciences/chifi/publis/pics/double/ref01645.png
M3 - 10.1021/acs.jpcc.9b10565
UR - http://dx.doi.org/10.1021/acs.jpcc.9b10565
N2 - A significant number of quadrupolar dyes with a D-Ï€-A-Ï€-D or A-Ï€-D-Ï€-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−À–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-Ï€-A-Ï€-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.
ID - 1645
ER -