Geometrically flexible synthetic manganese-oxygen and calcium-manganese-oxygen cubane clusters as reactive biomimics of the oxygen evolving complex of photosystem II.
Geometrically flexible synthetic manganese-oxygen and calcium-manganese-oxygen cubane clusters as reactive biomimics of the oxygen evolving complex of photosystem II.
复制标题
几何灵活的合成锰-氧和钙-锰-氧立方烷簇作为光系统 II 的放氧复合物的反应仿生体。
DOI：
10.1021/scimeetings.0c03947
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发表时间：
2020
期刊：
影响因子：
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通讯作者：
Michael J. Zdilla, Shivaiah Vaddypally
中科院分区：
文献类型：
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作者：
Michael J. Zdilla, Shivaiah Vaddypally
光系统 II 的放氧复合物 (OEC) 负责含氧光合生物中水向双氧的四电子氧化。这些生物体利用光驱动这一热力学上坡过程，从水中获取高能电子作为细胞能量，并产生氧气作为副产品。虽然 OEC 运作的许多细节已被充分了解，但 O=O 形成的分子机制仍存在争议。我们小组将展示复杂化学模型，其中我们制备了很少或没有末端多齿连接的簇系统，以生成几何灵活且具有反应性的簇。将展示两个系统：一系列具有可变钙含量的 Ca-Mn-O 半立方烷簇，以及它们在氧化反应中活化水的电催化活性，以及具有侧挂 Mn=O 部分的 Mn 立方烷簇，其从类似于自然系统转换状态的氧化态放出双氧
The oxygen evolving complex (OEC) of photosystem II is responsible for the four-electron oxidation of water to dioxygen in oxygenic photosynthetic organisms. These organisms use light to drive this thermodynamically uphill process to harvest high-energy electrons from water for cellular energy, generating O2 as a byproduct. While numerous details of the operation of the OEC are well understood, the molecular mechanism of O=O formation remains under debate. Model complex chemistry from our group will be presented wherein we have prepared cluster systems with little or no terminal multidentate ligation in order to generate geometrically flexible and reactive clusters. Two systems will be presented: a series of Ca-Mn-O hemicubane clusters with variable calcium content, and their electrocatalytic activity in activation of water in oxidation reactions, and a Mn cubane cluster with a pendant Mn=O moiety that evolves dioxygen from an oxidation state analagous to the turnover state of the natural system