Wei Jia, He Juan, Xu Gan, Chen Xu-Dong
State Key Laboratory of Microbial Technology, Jiangsu Collaborative Innovation Center of Biomedical Functional Materials, School of Chemistry and Materials Science, Nanjing Normal University (NNU), Nanjing, Jiangsu, 210023, China.
State Key Laboratory of Coordination Chemistry, Nanjing University (NJU), Nanjing, Jiangsu, 210093, China.
Angew Chem Int Ed Engl. 2025 Jun 24;64(26):e202504016. doi: 10.1002/anie.202504016. Epub 2025 May 26.
Iron-sulfur clusters are critical in a number of important biological processes, where their structural integrity can be maintained or reversibly transformed. However, it remains ambiguous how Fe-S clusters adapt to electrochemical demands for electron transport through redox-induced structural transformations. In this study, three Mo-Fe-S clusters comprising similar or distinct cores with [MoFe] metal centers in different oxidation states have been synthesized. These chemically interconvertible clusters exhibit strikingly similar cyclic voltammetry (CV) curves, irrespective of the structural differences in the core. Subsequent investigations indicate that the chloride ligand in cluster 2 is spontaneously replaced by the solvent molecule in solution and therefore only the solvent-ligated species exhibits an observable redox behavior that is almost identical to that of the chloride-free clusters 3 and 4. A comprehensive analysis of the redox behavior suggests that the intriguing redox events in the CV curves can be correlated to the electrochemical transformations between the chloride-free clusters. This work provides an insight into how Fe-S clusters maintain a stable redox behavior through structural transformations that can facilitate electron transfer in certain cases.
铁硫簇在许多重要的生物过程中至关重要，在这些过程中它们的结构完整性能够得以维持或发生可逆转变。然而，铁硫簇如何通过氧化还原诱导的结构转变来适应电子传输的电化学需求仍不明确。在本研究中，已合成了三个钼铁硫簇，它们具有相似或不同的核心，且[MoFe]金属中心处于不同氧化态。这些可化学相互转化的簇呈现出惊人相似的循环伏安（CV）曲线，无论核心结构存在差异。后续研究表明，簇2中的氯配体在溶液中会被溶剂分子自发取代，因此只有溶剂配位的物种表现出可观察到的氧化还原行为，该行为几乎与无氯簇3和4的氧化还原行为相同。对氧化还原行为的全面分析表明，CV曲线中有趣的氧化还原事件可与无氯簇之间的电化学转变相关联。这项工作深入揭示了铁硫簇如何通过结构转变来维持稳定的氧化还原行为，这种结构转变在某些情况下能够促进电子转移。
