Electrochemistry, spectroelectrochemistry and catalytic activity of biscobalt bisporphyrin dyads towards dioxygen reduction

Three face-to-face biscobalt bisporphyrin dyads, including one incorporating a copper(II) ion inside the linker, were synthesized and characterized both spectroscopically and electrochemically in three non-aqueous solvents, dichloromethane, benzonitrile and pyridine. The electrocatalytic reduction of dioxygen with these derivatives on an electrode surface in 1.0 M HClO4 was also investigated and the results are compared to that obtained with "regular" Pacman biscobalt bisporphyrins under the same experimental conditions. Surprisingly, the tris-metal species ( Cu-bisCo ) catalyzes the reduction of O2 mainly via a 2e- transfer process, leading to H2O2 , while the bis-metal (bisCo) catalyst p…