A model is presented for the electrostatic component of solvatochromic shifts on vertical electronic excitation energies. The model, called vertical electrostatic model 42 (VEM42), is based on representing the solute by a set of distributed atomic monopoles obtained by charge model 2 (CM2) and representing the solvent by its static and optical dielectric constants. The theory is applied here wi...

This work reports on the solvatochromic properties of a simple heterocyclic betaine pyridinium, 2-(1-pyridinio)benzimidazolate (SBPa), having promising potentialities in non-linear optics. From advanced PCM-TDDFT calculations, the solvatochromism of SBPa was found to be unusual, involving two different electronic states for absorption (S(0)→ S(2)) and emission (S(1)→S'(0)). To account for this ...

The optical properties of the dmit ion (dmits4,5-dimercapto-1,3-dithiol-2-thiolate) have been characterized under a range of conditions. The oxidatively sensitive anion is highly solvatochromic: lmaxs504 (H2O), 514 (MeOH), 568 (MeCN), and 632 nm (DMF). With a shift in absorption maximum of 4000 cm (DMF versus H2O), dmit 2y is possibly the most solvatochromic species known. The dianion is monopr...

Fluorescent pyrimidine analogs containing a fused biphenyl unit were prepared in high yields using stereoselective N-glycosylation and Suzuki-Miyaura cross-coupling reactions. The resulting "push-pull" fluorophores exhibit highly solvatochromic emissions from twisted intramolecular charge-transfer (TICT) states.

Two difluoroboron dipyrromethene (BODIPY) based fluorescent dyes - 4,4-difluoro-3-{2-[4-(dimethylamino)phenyl]ethenyl}-8-[4-(methoxycarbonyl)phenyl]-1,5,7-trimethyl-3a,4a-diaza-4-bora-s-indacene (1) and 4,4-difluoro-3-[2-(4-fluoro-3-hydroxyphenyl)ethenyl]-8-[4-(methoxycarbonyl)phenyl]-1,5,7-trimethyl-3a,4a-diaza-4-bora-s-indacene (3) - have been synthesized via condensation of p-N,N-dimethylami...

A 19F solvatomagnetic comparison of 4-fluorophenol and 4-fluoroanisole yields a more reliable measurement the hydrogen-bond acceptance ionic liquids green solvents than solvatochromic method.

The correspondence between the exact embedding potential and the pair of the electron densities--that of the embedded molecule and that of its environment [Wesolowski and Warshel, J. Phys. Chem. 1993, 97, 8050]--is used to generate the average embedding potential and to subsequently calculate the solvatochromic shifts in a number of organic chromophores in solvents of various polarities. The av...

We study the solvent-induced frequency shifts of the OH-stretching mode of 1-naphthol and 2-naphthol in nonpolar/weakly polar solvents, subject to electronic excitation, with ultrafast UV/mid-infrared pump-probe spectroscopy and theoretical modeling based on Pullin's perturbative treatment of vibrational solvatochromic effects. The model is parametrized at the density functional theory (DFT) le...

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 ...