LAUSR

In his pioneering work to unravel the catalytic power of enzymes, Warshel has pertinently validated that electrostatic interactions play a major role in the activation of substrates. Implementing such chemical artifice in molecular catalysts may help improve their catalytic properties. In this study, we have designed a series of tetra- , d i- and mono -substituted iron porphyrins with cationic imidazolium groups. Their presence in the second coordination sphere help stabilize the [Fe-CO 2 ] intermediate through electrostatic interactions. We found herein that the electrocatalytic overpotential is a function of the number of embarked imidazolium. Importantly, we evidenced a gain of six orders of magnitude in turnover frequencies going from a tetra - to a mono -substituted catalyst. Furthermore, our comparative study shows that catalytic performances trend of through-space electrostatic interaction, a first topological effect reported for iron porphyrins, outperforms the classical through-structure electronic effect.