Article

Abstract

The electron transfer photochemistry of 2,3-dicyanonaphthalene has been studied by a combination of fluorescence and transient absorption spectroscopy. The singlet excited state has a lifetime of 26 ns in acetonitrile and reacts with aromatic and alkene donors with oxidation potentials less than ~1.8 V with rate constants that are close to the diffusion-controlled limit. Transient absorption measurements demonstrate that the fluorescence quenching leads to efficient formation of free-radical ions. The radical ion yields have been measured for several donors and are compared to those for the more commonly used sensitizer, 1.4-dicyanonaphthalene. In the absence of added donors, direct excitation of 2,3-dicyanonaphthalene provides evidence for photoionization at high laser energy, in addition to triplet formation. The results illustrate the utility of this sensitizer for photoinduced electron transfer reactions.Key words: photoinduced electron transfer, laser flash photolysis, fluorescence, photosensitizers.