Electrochemical and spectroelectrochemical characterization of Cu(II) and Mn(III) tetrabutano- and tetrabenzoporphyrins containing sterically hindered meso -(2,6-difluorophenyl) substituents in nonaqueous media

Four tetrabutano and tetrabenzoporphyrins containing sterically hindered meso-(2,6-difluorophenyl) substituents and copper(II) or manganese(III) central metal ions were synthesized and characterized as to their electrochemical and spectroelectrochemical properties in nonaqueous media. The copper(II) derivatives exhibit the expected two one-electron reductions to give [Formula: see text]-anion radicals and dianions in CH2Cl2. Electrochemical and spectroelectrochemical data suggest that a Cu(II) phlorin anion is generated from the doubly reduced Cu(II) butanoporphyrin and it is this species which undergoes the third reduction in pyridine. The first one-electron reduction of the Mn(III) porphyrins is metal-centered to give a Mn(II) compound, while the second and third reductions are macrocycle-centered to give Mn(II) porphyrin [Formula: see text]-anion radicals and dianions in both CH2Cl2 and pyridine. A Mn(II) phlorin anion is also generated from the Mn(II) dianion on the spectroelectrochemical timescale under the given solution conditions. The [Formula: see text],[Formula: see text]-butano and benzo groups have a significant effect on the measured redox potentials. Steric hindrance of the meso-(2,6-difluorophenyl) substituents also has an effect on the potential separation between the first two oxidations of the benzoporphyrins.