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PHOTOSENSITIZATION VIA CHARGE TRANSFER OR REVERSIBLE ELECTRON TRANSFER. OXIRANE ISOMERIZATION AND SULFUR DIOXIDE EXTRUSION
Author(s) -
DAS P. K.,
MULLER A. J.,
GRIFFIN G. W.,
GOULD I. R.,
TUNG C.H.,
TURRO N. J.
Publication year - 1984
Publication title -
photochemistry and photobiology
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.818
H-Index - 131
eISSN - 1751-1097
pISSN - 0031-8655
DOI - 10.1111/j.1751-1097.1984.tb08178.x
Subject(s) - isomerization , photochemistry , chemistry , intersystem crossing , electron transfer , singlet state , acetonitrile , extrusion , intramolecular force , electron , singlet oxygen , excited state , stereochemistry , organic chemistry , materials science , oxygen , catalysis , physics , quantum mechanics , metallurgy , nuclear physics
— N, N, N ′ N ′ ‐Tetramethylbenzidine (NTMB) photosensitizes the cis‐trans isomerization of stilbene oxiranes (SO) and the extrusion of SO 2 from dibenzyl sulfone (DBS). In acetonitrile solution it is found that in the absence of SO or DBS, singlet NTMB undergoes three processes: intersystem crossing to triplet NTMB (φ ISC = 0.63, k ISC = 6.3 × 10 7 s ‐1 ), fluorescence (φ f = 0.30, k f = 3 × 10 7 s ‐1 ), and formation of a cation by electron ejection (φ ion = 0.09). Both singlet and triplet sensitization are observed. A charge transfer or reversible electron transfer mechanism is proposed to explain the results.