Journal
JOURNAL OF PHYSICAL ORGANIC CHEMISTRY
Volume 24, Issue 4, Pages 274-281Publisher
WILEY-BLACKWELL
DOI: 10.1002/poc.1744
Keywords
donor-acceptor system; solvatochromism; solvent effects; UV/Vis spectroscopy
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Funding
- Ministry of Education, Youth and Sport of the Czech Republic [MSM 0021627501]
- ETH Research Council
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A representative data set has been gained by the measurement of the electronic absorption spectra of 12 systematically selected push-pull systems with an intramolecular charge-transfer (CT) absorption and the general structure D-pi-A (D = donor, A = acceptor) featuring electron-withdrawing CN groups, electron-donating N(CH(3))(2) groups, and various p-conjugated backbones in 32 solvents with different polarities. The longest-wavelength absorption maxima lambda(max) and the corresponding wavenumbers (v) over tilde (max) were evaluated from the UV/Vis spectra measured in 32 well-selected solvents. The D-pi-A push-pull systems were further characterized by quantum-chemical quantities and simple structural parameters. Structure-solvatochromism relationships were evaluated by multidimensional statistic methods. Whereas solvent polarizability and solvent cavity size proved to be the most important factors affecting the position of lambda(max), the solvent polarity was less important. The most important characteristics of organic CT compounds are the energy of the LUMO, the permanent dipole moment, the COSMO (COnductor-like Screening MOdel) area, the COSMO volume, the number, and ratio of N,N-dimethylamino and cyano groups, and eventually the number of triple bonds (pi-linkers). A relation between the first-order polarizability alpha, the longest-wavelength absorption maxima lambda(max), and the structural features has also been found. The higher-order polarizabilities beta and g are not related to the observed solvatochromism. Copyright (C) 2010 John Wiley & Sons, Ltd.
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