Molecular structures and electronic transitions of 3,6-diphenyl-1,2-dithiin and its radical cation: a spectroelectrochemical and DFT study.
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.
Hennig
Horst
H
Institut für Anorganische Chemie and Wilhelm-Ostwald-Institut für Physikalische und Theoretische Chemie, Universität Leipzig, Johannisallee 29, D-04103 Leipzig, Germany. hennigho@chemie.uni-leipzig.de
Schumer
Frank
F
Reinhold
Joachim
J
Kaden
Heiner
H
Oelssner
Wolfram
W
Schroth
Werner
W
Spitzner
Roland
R
Hartl
Frantisek
F
D002412:Cations / Q000737:chemistry; D004563:Electrochemistry; D004583:Electrons; D005609:Free Radicals / Q000737:chemistry*; D015394:Molecular Structure; D013057:Spectrum Analysis; D013440:Sulfides / Q000737:chemistry*
D002412:Cations; D005609:Free Radicals; D013440:Sulfides