Redox properties of bis-cobalt(III) complex of 3,3′-linked N-confused porphyrin dimer with axial pyridine ligands

Abstract

Novel cobalt(III) complexes of N-confused porphyrin (5,10,15,20-tetrakis(penta-fluorophenyl)-2-aza-21-carbaporphyrin) and its 3,3[Formula: see text]-linked dimer, Co1 and Co2, were synthesized and their structures were elucidated by X-ray crystallographic analysis and NMR spectroscopy. The redox properties of the complexes were examined by electrochemical approaches, and the corresponding oxidized/reduced species were analyzed by spectroelectrochemistry and DFT calculations. Notably, due to the facile redox feature of the N-confused porphyrins, ligand-centered oxidative/reductive processes were assumed for Co1 and Co2 presumably as inferred from the spectral analyses. These results indicate the unique multi-electron reservoir capability of the metal complexes of the N-confused porphyrin dimer.