Influence of the proton relay spacer on hydrogen electrocatalysis by cobalt hangman porphyrins

A cobalt hangman porphyrin system with a phenyl spacer between the porphyrin ring and an internal carboxylic acid group as well as its non-hangman analogue were synthesized and utilized for the study of the proton-coupled electron transfer (PCET) kinetics attendant to electrocatalytic hydrogen evolution. Cyclic voltammetry (CV) together with simulations show that a short distance between the proton relay and the redox active cobalt center as well as the increased proton donating strength results in superior catalytic activity. The mechanism of hydrogen generation is at the nexus of proton transfer–electron transfer (PTET) and concerted proton–electron transfer (CPET), as opposed to an ETPT mechanism that is characteristic of hangman systems with longer proton relay networks.