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Electronic Spectra of Cycl[3.3.2]azine and Related Compounds: Solvent Effect on Vibronic Couplings
journal contribution
posted on 2012-09-13, 00:00 authored by Yasuhiro Shigemitsu, Motoyuki Uejima, Tohru Sato, Kazuyoshi Tanaka, Yoshinori TominagaQuantitative ab initio calculations are presented for
the ultraviolet–visible
peaks of cycl[3.2.2]azine and its mono- and dibenzannulated polycyclic
compounds at the multistate CASPT2 (MS-CASPT2) level of theory, with
11 nm deviation from the experimental S0 → S1 absorption. The electrophilic substitution reactions of cycl[3.2.2]azine,
benzo[a]/[g]annulated cycl[3.2.2]azines,
and 6-dimethylamino[2.2.3]cyclazine-1-carboxylates with 3-cyano-4-methylthiomaleimide
gave the corresponding functionalized cycl[3.2.2]azine derivatives,
which exhibited the absorption maxima around 510–630 nm. The
first intense peaks were investigated by means of time-dependent density
functional theory (TD-DFT). These peaks were systematically underevaluated
by ∼50 nm, within the acceptable accuracies of TD-DFT. Furthermore,
we calculated vibronic coupling constants of the electronic excited
states of cycl[3.2.2]azine and simulated absorption spectra both in
vacuo and in ethanol. The solvent effect is found to enhance oscillator
strengths and vibronic couplings. This is because the solvent effect
gives rise to changes in the electron density difference on the phenyl
ring, and in turn, the intensified overlap between the electron density
difference and the potential derivative in the phenyl ring leads to
enhanced vibronic couplings in ethanol.