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- Title
Through‐Space Electrostatic Interactions Surpass Classical Through‐Bond Electronic Effects in Enhancing CO<sub>2</sub> Reduction Performance of Iron Porphyrins.
- Authors
Khadhraoui, Asma; Gotico, Philipp; Leibl, Winfried; Halime, Zakaria; Aukauloo, Ally
- Abstract
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, a series of tetra‐, di‐, and mono‐substituted iron porphyrins with cationic imidazolium groups were designed. Their presence in the second coordination sphere helped stabilize the [Fe−CO2] intermediate through electrostatic interactions. It was found herein that the electrocatalytic overpotential is a function of the number of embarked imidazolium. Importantly, a gain of six orders of magnitude in turnover frequencies was observed going from a tetra‐ to a mono‐substituted catalyst. Furthermore, the comparative study showed that catalytic performances trend of through‐space electrostatic interaction, a first topological effect reported for iron porphyrins, outperforms the classical through‐structure electronic effect.
- Subjects
IRON porphyrins; ELECTROSTATIC interaction; POLAR effects (Chemistry); METALLOPORPHYRINS; ZINC porphyrins; MAGNITUDE (Mathematics); OVERPOTENTIAL
- Publication
ChemSusChem, 2021, Vol 14, Issue 5, p1308
- ISSN
1864-5631
- Publication type
Article
- DOI
10.1002/cssc.202002718