Molecular structures and electronic transitions of 3,6-Diphenyl-1,2-dithiin and its radical cation: a spectroelectrochemical and DFT study

Hennig, H., Schumer, F., Reinhold, J., Kaden, H., Oelssner, W., Schroth, W., Spitzner, R. and Hartl, F. ORCID: https://orcid.org/0000-0002-7013-5360 (2006) Molecular structures and electronic transitions of 3,6-Diphenyl-1,2-dithiin and its radical cation: a spectroelectrochemical and DFT study. The Journal of Physical Chemistry A, 110 (5). pp. 2039-2044. ISSN 1089-5639 doi: 10.1021/jp0551059

Abstract/Summary

One-electron oxidation of 3,6-diphenyl-1,2-dithiin yields the corresponding radical cation. The product is stable at low temperatures and can be distinguished by a triplet EPR signal. Cyclic voltammetric, UV-vis spectroelectrochemical, and DFT studies were performed to elucidate its molecular structure and electronic properties. Time-dependent DFT calculations reproduce appreciably well the UV-vis spectral changes observed during the oxidation. The results reveal a moderately twisted structure of the 1,2-dithiin heterocycle in the radical cation.