Studies of the electron-transfer photochemistry of arene-iminium salt systems have been explored. Fluorescence quenching investigations have demonstrated that a series of arenes including substituted toluenes and benzenes quench the fluorescence of a variety of 2-aryl-I-pyrrolinium perchlorates. Quenching rate constants in these cases correlate with the ACsET values as expected for quenching by reversible electron-transfer pathways. In addition, nonconjugated iminium salts quench the fluorescence of a host of arenes with k, values which parallel those predicted on the basis of electron-transfer free energy calculations. Photoaddition reactions of toluene, benzyltrimethylsilane, benzyltrimethylstannane, and 2-aryl-1 -pyrroliniurn salts have been explored. Likewise, electron-transfer-induced, excited-state reactions of toluene and benzyltrimethylsilane with 1,2-dimethyl-l-pyrrolinium perchlorate have been investigated. The results of these photoreactions have been interpreted in terms of steric, electrofugal group, and solvent effects upon the rates of competitive pathways available to initially formed radical cation pair intermediates. Finally, the photochemistry of benzyltrimethylstannane is described.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.