Photorelease of carboxylic and amino acids from N-methyl-4-picolinium esters by mediated electron transfer

Abstract

One electron reduction of N-alkyl-4-picolinium (NAP) esters initiates C–O bond scission releasing a carboxylate anion. Previous experiments have demonstrated that this process can be initiated by photoinduced electron transfer from an electron-donating sensitizer. In the present study it is demonstrated that a comparable photorelease process can be initiated by photolysis of an electron acceptor (mediator), which in turn abstracts an electron from a ground state electron donor. The resulting mediator anion radicals donate an electron to the NAP ester, triggering release of the carboxylate anion. It is demonstrated that when benzophenone is used as a mediator, higher quantum yields for ester decomposition can be achieved compared with sensitizers that do direct photoinduced electron transfer.