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Novel cationic diaza-, azaoxo-, and dioxo[6]helicenes are readily prepared and functionalized selectively by orthogonal aromatic electrophilic and vicarious nucleophilic substitutions (see scheme). Reductions, cross-coupling, or condensation reactions introduce additional diversity and allow tuning of the absorption properties up to the near-infrared region. The diaza salts can be resolved into single enantiomers. | ||||||||
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The mechanoelastic model is applied to reproduce the experimental relaxation and thermal transition curves as determined for crystals of pure and diluted {[FexZn1–x(bbtr)3](ClO4)2}∞ [bbtr = 1,4-di(1,2,3-triazol-1-yl)butane] spin-crossover systems. In the mechanoelastic model, the spin-crossover complexes are situated in a hexagonal planar lattice, which is similar to the 2D coordination polymer with (3,6) network topology of [Fe(bbtr)3](ClO4)2. These complexes are linked by springs, which simulate the elastic interactions between them. Owing to the change in volume of the complexes during the spin transition, an elastic force accompanies the switch of every complex. This force propagates through the entire lattice and causes a shift of all molecules in the system and thus results in a new nuclear configuration. First, the ability of the model to reproduce various shapes of thermal transition and relaxation curves in pure compounds is analyzed; these range from gradual to very steep and include hysteresis behavior for the former and from single exponential to sigmoidal or with several steps for the latter. A structural phase transition can also be accounted for by changing the shape of the sample at a fixed temperature from a regular to an elongated hexagon. Furthermore, the effect of adding Zn as a dopant in a mixed crystal series is discussed. The role of dopants on the cluster evolution is also analyzed directly and by using the correlation factor. | ||||||||
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The synthesis and photophysical properties of the complex [Fe(phen)2(TTF-dppz)]2+ (TTF-dppz = 4′,5′-bis-(propylthio)tetrathiafulvenyl[i]dipyrido[3,2-a:2′,3′-c]phenazine, phen = 1,10-phenanthroline) are described. In this complex, excitation into the metal–ligand charge transfer bands results in the population of a high-spin state of iron(II), with a decay lifetime of approximately 1.5 ns, in dichloromethane, at room temperature. An intraligand charge transfer state can also be obtained and has a lifetime of 38 ps. A mechanism for the different states reached is proposed based on transient absorption spectroscopy. | ||||||||
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The excited-state dynamics of two triads consisting of a naphthalenediimide (cNDI) substituted at the core by two zinc (ZnP) or free-base tetraphenylporphyrins (FbP) was investigated by ultrafast fluorescence and transient absorption spectroscopy. The electronic absorption spectra of the triads are almost the composites of those of the constituents, pointing to a weak electronic coupling and to a localization of the excitation energy on one of the porphyrins. In cyclohexane, the excited-state dynamics of the triads are essentially the same as those of the individual porphyrins, with the exception of the Soret emission of the ZnP triad, whose lifetime exhibits a more than 10 fold shortening compared to ZnP. A similarly ultrafast fluorescence decay was measured in tetrahydrofuran and benzonitrile. In these two solvents, charge separation from the excited porphyrin to the cNDI was found to take place with ~1 ps and ~25 ps time constants in the ZnP and FbP triads, respectively. The build up of the charge-separated state population in the ZnP triad is independent on the excitation wavelength, indicating that charge separation takes place from the lowest singlet excited state. Charge recombination occurs with a time constant around 8 ps in both triads, i.e. is slower than charge separation in the ZnP triad but faster in the FbP triad. These differences are rationalized in terms of the driving forces for charge separation and recombination. | ||||||||
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The absorption spectrum of fluorenone in zeolite L is calculated from first-principles simulations. The broadening of each band is obtained from the explicit treatment of the interactions between the chromophore and its environment in the statistical ensemble. The comparison between the simulated and measured spectra reveals the main factors affecting the spectrum of the chromophore in hydrated zeolite L. Whereas each distinguishable band is found to originate from a single electronic transition, the bandwidth is determined by the statistical nature of the environment of the fluorenone molecule. The K+...O=C motif is retained in all conformations. Although the interactions between K+ and the fluorenone carbonyl group result in an average lengthening of the C=O bond and in a redshift of the lowest energy absorption band compared to gas phase or non-polar solvents, the magnitude of this shift is noticeably smaller than the total shift. An important factor affecting the shape of the band is fluorenone’s orientation, which is strongly affected by the presence of water. The effect of direct interactions between fluorenone and water is, however, negligible. | ||||||||
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The emission spectra of Sm2+ doped in BaFBr and SrFBr hosts were measured at 10 K from ambient pressure to 8 GPa. The crystal field energy levels determined from the emission spectra were used to extract the free ion parameters (Fk and ζ ) and crystal field parameters (Bqk). The variation of Fk and ζ as a function of pressure was studied systematically and was discussed in relation to the central field and symmetry restricted covalency models. The change of the spin orbit coupling parameter (ζ) with pressure for SrFBr:Sm2+ showed very different behavior than in other matlockite hosts. Moreover the variation of Bqk under pressure was studied. The pressure dependence of the Bqk was described quantitatively using the Superposition Model (SM) with the help of structural parameters as a function of pressure, obtained from periodic DFT calculations. The validity of the SM was tested for Sm2+ in BaFBr and SrFBr. It is shown that this model does not apply to SrFBr, in contrast to other matlockite host materials. | ||||||||
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Chromium(III)-trisoxalate,[Cr(ox)3]3- (ox = C2O42-), incorporated into polymeric networks of composition [NaCr(ox)3][MII(bpy)3] and [NaCr(ox)3][MIII(bpy)3]ClO4 (bpy= 2,2'-bipyridine, MII = Zn, Fe, Ru; MIII = Rh, Cr), results in interesting features ranging from phonon-assisted and resonant energy migration within the R1 line the 2E state to persistent spectral side-hole burning via the latter, and manifestations of specific nearest-neighbour π–π interactions between bipyridine and oxalate. | ||||||||