Abstract
Laser excitation of CoIITPP within the Soret absorption band in the presence of p-benzoquinone (p-BQ) results in oxidation of the complex. Oxidation occurs both at the metal center and the porphyrin ring depending upon the experimental conditions. Under anaerobic conditions, oxidation takes place at the metal center to produce the cobaltic species CoIII( TPP )+, while in the presence of molecular oxygen oxidation also occurs at the porphyrin ring giving CoIII( TPP )2+•cation radical as oxidation product. From the inhibiting effect of peroxy radical trapping agent on the photooxidation of CoIITPP under aerobic conditions, the two-electron oxidation is suggested to involve solvent radicals and we discuss the mechanistic details of the process in this work.
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