Electrochemical, spectroelectrochemical and ESR spectroscopic characterization of 2,3- and 3,4-cobalt tetrapyridoporphyrazine isomers in non-aqueous media

Abstract

Two cobalt porphyrazines, 2,3-tetrapyridoporphyrazine and 3,4-tetrapyridoporphyrazine, were examined in N,N-dimethylformamide, dimethyl sulfoxide and pyridine solutions as to their electrochemical, spectroelectrochemical and ESR spectroscopic properties. These results were compared with those of the unsubstituted cobalt phthalocyanine. At high concentrations, aggregation was observed for each investigated compound in the three solvents. The intensity of ESR signals of each derivative depends upon the extent of aggregation in its solution. The g values shift towards high field with an increase in the strength of the axial ligand and the number of axial ligands on the cobalt center. Both tetrapyridoporphyrazine complexes undergo one oxidation and three reductions in N,N-dimethylformamide, dimethyl sulfoxide or pyridine solution. Thin-layer UV-visible spectroelectrochemical results confirmed that the first oxidation and first reduction of both compounds are metal-centered while the second and third reductions are ring-centered. An overall electron transfer mechanism for both porphyrazine derivatives is proposed.