PHOTOSENSITIZATION VIA CHARGE TRANSFER OR REVERSIBLE ELECTRON TRANSFER. OXIRANE ISOMERIZATION AND SULFUR DIOXIDE EXTRUSION |
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| Authors: | P K DAS A J MULLER† G W GRIFFIN† I R GOULD† C-H TUNG† N J TURRO† § |
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| Institution: | *Radiation Laboratory, University of Notre Dame, South Bend, IN 46556, USA;†University of New Orleans–Lakefront, New Orleans, LA 70148, USA;†Chemistry Department, Columbia University New York, NY 10027, USA |
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| Abstract: | Abstract— N, N, N' N'-Tetramethylbenzidine (NTMB) photosensitizes the cis-trans isomerization of stilbene oxiranes (SO) and the extrusion of SO2 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 (φISC= 0.63, k ISC= 6.3 × 107s-1), fluorescence (φf= 0.30, k f= 3 × 107s-1), and formation of a cation by electron ejection (φion= 0.09). Both singlet and triplet sensitization are observed. A charge transfer or reversible electron transfer mechanism is proposed to explain the results. |
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