Substituted phthalocyanine-sensitized photochemical generation of superoxide anion radical.

The quantum yield of phthalocyanine-photosensitized generation of superoxide anion radical (O2-) was measured by the electron spin resonance (ESR) technique. From the redox potential data, it is concluded that O2- is formed by electron transfer from the singlet excited state (not triplet or ground state) of phthalocyanines (PCs) to oxygen. Since a much larger theoretical quantum yield of O2- generation (phi c) than experimental (phi m) was found, it is suggested that charge recombination processes between O2- and PCs+ occur more rapidly than O2- trapping by 5,5-dimethyl-1-pyrroline-1-oxide (DMPO). The results indicate that the use of DMPO as a spin trap is not an ideal method for measurement of the quantity of O2- formed via photosensitization.