The electronic structure, absorption and emission spectra, aromaticity and photophysical behavior of the recently synthesized tetrasilatetrathiacirculene and tetragermatetrathiacirculene compounds have been studied computationally. Both compounds demonstrate a specific bifacial aromaticity, which is unusual for heterocirculenes; the inner eight-membered core sustains an expected strong paratropic magnetically-induced ring current, while the outer perimeter contains saturated Si(Et) 2 and Ge(Et) 2 moieties which break the conjugation between the thiophene rings. The overall magnetically-induced ring current for both studied circulenes is close to zero because of the strong local diatropic currents in each thiophene ring that compensate the paratropic counterpart. The electronic absorption and emission spectra of tetrasilatetrathiacirculene and tetragermatetrathiacirculene demonstrate a clear visible vibronic progression. The 0-0 band is the most active one in the absorption spectra, while in the fluorescence spectra the 0-1 band composed of several normal vibrations is more intense compared with the 0-0 band in excellent agreement with experiment. Accounting for spin-orbit coupling effects, an analysis of the photophysical constants for the two compounds demonstrates: (1) a clear manifestation of the internal heavy atom effect on the inter-system crossing efficiency; (2) one to two order domination of non-radiative rates over the fluorescence rate; and (3) that the S 1 -S 0 internal conversion is extremely slow and can not compete with the fluorescence, while the S 1 -T n inter-system crossing is a main deactivation channel of the S 1 excited state. These results provide new insight into the electronic structure and photophysics of tetrasilatetrathiacirculene and tetragermatetrathiacirculene as novel standalone representatives of heterocirculenes-tetraannelated derivatives of tetrathienylene.
ASJC Scopus subject areas
- Physics and Astronomy(all)
- Physical and Theoretical Chemistry