Photoinduced electron transfer reactions of pyrylium derivatives with organic sulfides in acetonitrile

The photochemistry and photophysics of pyrylium derivatives with organic sulfides in acetonitrile medium are investigated. A steady decrease in the fluorescence intensity and fluorescence lifetime of the dyes was observed with increase in the quencher concentration. Bimolecular quenching constants were evaluated and correlated with the free energy of electron transfer. Laser flash photolysis investigations on the dyes in presence of quenchers were done. Observation of pyranyl radical and sulfide cation radicals as intermediates clearly illustrates the electron transfer mechanistic pathway for this reaction. The radical pair energies were calculated and found to be lower than the triplet energy of the sensitisers and hence we do not see any triplet induction in the present system. (c) 2008 Elsevier B.V. All rights reserved.