Electrocatalytic hydrogen evolution with a copper porphyrin bearing meso -( o -carborane) substituents.

A newly designed copper complex of 5,15-bis(pentafluorophenyl)-10,20-bis( o -carborane)porphyrin (1) was synthesized and tested for the electrocatalytic hydrogen evolution reaction (HER). In acetonitrile, 1 was much more efficient than Cu 5,15-bis(pentafluorophenyl)-10,20-diphenylporphyrin (2) for electrocatalytic HER by shifting the catalytic wave to the anodic direction by 190 mV. In aqueous media, 1 also outperformed 2 by achieving higher current densities under smaller overpotentials. This enhancement was attributed to the aromatic and the strong electron-withdrawing properties of o -carborane groups. This work is significant to address the crucial effects of meso -( o -carborane) substituents of metal porphyrins on boosting the electrocatalytic HER.