Abstract
Abstract Chloro(5,10,15,20-tetraphenylporphyrinato)cobalt(III), CoIII(tpp)Cl, in an aerated dichloromethane(DCM) solution undergoes photooxidation to produce the porphyrin π-cation radicals, CoIII(tpp)+·Cl2. The formation mechanism of the π-cation radical was investigated by means of optical absorption and ESR spectroscopy: CoIII(tpp)Cl in DCM decomposes photochemically to yield CoII(tpp) and chlorine atoms, which then abstract hydrogen atoms from DCM molecules to yield solvent radicals, ·CHCl2, and HCl. The solvent radicals react with oxygen molecules, resulting in the generation of peroxyl radicals, which then oxidize CoIII(tpp)Cl to produce the π-cation radicals, CoIII(tpp)+·Cl2.
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