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

Novel cobalt(III) complexes of N-confused porphyrin (5,10,15,20-tetrakis(pentafluorophenyl)-2-aza-21-carbaporphyrin) and its 3,3'-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.

Automated summary

Novel cobalt(III) complexes of N-confused porphyrin and its dimer were synthesized and their structures were elucidated. The redox properties of the complexes were examined using electrochemical approaches, spectroelectrochemistry, and DFT calculations. The results indicate the unique multi-electron reservoir capability of the metal complexes of the N-confused porphyrin dimer.