Through?Space Electrostatic Interactions Surpass Classical Through?Bond Electronic Effects in Enhancing CO ₂ Reduction Performance of Iron Porphyrins

In his pioneering work to unravel the catalytic power of enzymes, Warshel has pertinently validated that electrostatic interactions play a major role in activation substrates. Implementing such chemical artifice molecular catalysts may help improve their properties. this study, series tetra-, di-, and mono-substituted iron porphyrins with cationic imidazolium groups were designed. Their presence second coordination sphere helped stabilize [Fe?CO2] intermediate through interactions. It was found herein electrocatalytic overpotential is function number embarked imidazolium. Importantly, gain six orders magnitude turnover frequencies observed going from tetra- catalyst. Furthermore, comparative study showed performances trend through-space interaction, first topological effect reported for porphyrins, outperforms classical through-structure electronic effect.