Abstract
Light-induced electron transfer reactions from phenolate ions to a variety of carbonyl triplets have been studied in aqueous acetonitrile by using 337.1-nm laser flash photolysis. In particular, the effects of carbonyl triplet nature and substitution in phenolate ions have been examined with respect to both kinetics and primary photoproduct yields. The rate constants for electron transfer are found to be in the range 2 x 10/sup 9/-1 x 10/sup 10/ M/sup -1/ s/sup -1/. The quantum yields of primary photoproducts (phenoxy radicals and radical anions of carbonyl compounds) are essentially unity except with p-bromo- and p-iodophenolate ions. With p-iodophenolate ion, the yields of ketone-derived radical ions are in the range 0.3 to 0.5 and remain practially unchanged on increasing the temperature from 23 to 75/sup 0/C. This result suggests the involvement of heavy atom induced intersystem crossing and/or back electron transfer at some stage(s) of the electron transfer reaction mechanism. 6 figures, 4 tables.
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