Dataset of "Dynamic Binding of Alkali-Metal Ions in a Metalloporphyrin Cage: Impact on Redox Properties"

The influence of local electrostatic environments on catalytic reactivity is well established in enzymatic systems, but their systematic implementation in synthetic catalysts remains limited. Here, we investigate the dynamic binding of alkali-metal cations to a cobalt porphyrin cage complex as a strategy to modulate its redox properties and catalytic activity toward CO2 reduction (CO2RR). Electrochemical studies reveal that the Co¹+ → Co0 redox potential is highly sensitive to the identity of the electrolyte cation, with K+ and Cs+ inducing the largest positive shifts (236 mV and 225 mV, respectively), resulting in substantial decreases in CO2RR overpotential. In contrast, Li+, Na+, and Ca²+ produce only minor or moderate effects. Molecular dynamics simulations rationalize these observations in terms of binding mode and dynamics: Li+ remains fully solvated, Na+ interacts weakly with the cage, while K+ and Cs+ bind specifically and symmetrically to the ether-functionalized cage walls, with oxidation state-dependent occupancy. These findings illustrate how alkali-metal ion coordination can be harnessed to modulate molecular electrocatalysts and guide the design of redox-tunable systems.局部静电环境对催化反应活性的影响在酶体系中已得到充分证实，但其在合成催化剂中的系统性应用仍十分有限。本研究以碱金属阳离子与钴卟啉笼状配合物的动态结合为策略，探究其对该配合物氧化还原特性及二氧化碳还原（CO2RR）催化活性的调控作用。电化学研究表明，Co¹+ → Co⁰的氧化还原电位对电解质阳离子的种类具有高度敏感性：K+与Cs+可引发最大幅度的正移（分别为236 mV与225 mV），进而使CO2RR过电位显著降低。相比之下，Li+、Na+与Ca²+仅产生微弱或中等程度的影响。分子动力学模拟从结合模式与动态行为层面为上述实验现象提供了合理解释：Li+始终保持完全溶剂化状态，Na+仅与笼状结构发生弱相互作用，而K+与Cs+则可特异性且对称地结合至醚功能化的笼壁上，其结合占有率随氧化还原态变化而改变。本研究结果表明，可通过碱金属离子配位策略调控分子电催化剂，并为氧化还原可调谐体系的设计提供指导。