Artificial Mn4-oxido complexes mimic the oxygen-evolving center in photosynthesis
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摘要:
The understanding of the structure-function relationship of the oxygen-evolving center (OEC),a Mn4Cacluster,in photosystem Ⅱ is impeded mainly due to the complexity of the protein environment and lack of rational chemical models as a reference.In this study,two novel Mn4-oxido complexes have been synthesized and characterized,in which the peripheral ligands of the [MnⅢ4] core are provided by eight μ2-carboxylate groups and two neutral terminal ligands (pyridine or isoquinoline).This type of peripheral ligation is very similar to the Mn4Ca-oxide model complexes recently reported to mimicthe OEC.The new Mn4-oxide complex can catalyze the oxygen-evolving reaction in the presence of ButOOH as an oxidant.The structure and redox properties comparison of the Mn4-oxido and Mn4Ca-oxido complexes provide important clues to understanding the functional role of Ca in the OEC in natural photosynthesis,and develop more efficient artificial catalysts for the water-splitting reaction in the future.