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.

中文翻译：

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在增强铁卟啉的CO2还原性能方面，穿越空间的静电相互作用超越了经典的贯穿键电子效应。

在揭开酶催化能力的开创性工作中，沃舍尔恰当地验证了静电相互作用在底物活化中起着重要作用。在分子催化剂中实施此类化学手段可能有助于改善其催化性能。在这项研究中，设计了一系列带有阳离子咪唑鎓基团的四，二和单取代铁卟啉。它们在第二个协调领域的存在有助于稳定[Fe-CO ₂通过静电相互作用产生的中间体。在本文中发现，电催化超电势是所着装的咪唑鎓的数量的函数。重要的是，从四取代催化剂到单取代催化剂，观察到周转频率增加了六个数量级。此外，比较研究表明，贯穿空间的静电相互作用的催化性能趋势是铁卟啉的首个拓扑效应，其性能优于经典的贯穿结构的电子效应。