Photosensitized electron transfer from sterically hindered amines to the benzophenone triplet and its reversion in solvents of different polarity

The reductive quenching of the benzophenone triplet by 2,2,6,6-tetramethyl- and 1,2,2,6,6-pentamethyl-piperidine was studied by laser flash photolysis. The rate constants for the quenching process were obtained in solvents of different polarity, acetonitrile, methanol, acetone, n-butanol, t-butanol, butyl chloride, chloroform, 1,4-dioxane, cyclohexane and benzene. The contact ion pair primarily formed, decays by proton transfer under the formation of the benzophenone ketyl radical, back electron transfer and charge separation. In our experiments no indication for the free solvated anion radical was found. The ketyl radical yields vary with solvent polarity, showing a minimum for the solvent butyl chloride. We explain this behaviour in terms of the solvent dependence of the back electron transfer process. Rate constants were determined for all reactions studied.