Through-Space Electrostatic Effects of Positively Charged Substituents on the Hydrogen Evolution Reaction.

Elucidating the effects of various structural components on energy-related small molecule activation is of fundamental and practical significance. Herein the inhibition effect of positively charged substituents on the hydrogen evolution reaction (HER) was reported. With the use of Cu porphyrins 1-5 containing different numbers and locations of positively charged substituents, it was demonstrated that their electrocatalytic HER activities significantly decreased when more cationic units were located close to the Cu ion: the i /i (i is the catalytic peak current, i is the one-electron reduction peak current) value decreased from 38 with zero cationic unit to 15 with four closely located cationic units. Inspired by this result, Cu porphyrin 6, with four meso-phenyl groups each bearing a negatively charged para-sulfonic substituent, was designed. With these anionic units, 6 outperformed the other Cu porphyrins for electrocatalytic HER under the same conditions.