Artificial Mn4Ca‐cluster with Exchangeable Solvent Molecules Mimicking the Oxygen‐Evolving Center in Photosynthesis

The natural Mn4Ca‐cluster in photosystem II serves as a blueprint to develop artificial water‐splitting catalysts for the generation of solar fuel in artificial photosynthesis. Although significant advances have recently been achieved, it remains great challenges to prepare robust artificial Mn4Ca‐cluster to precisely mimic the structure and function of the biological catalyst in the laboratory. Here, we report the isolation and structural characterization of two Mn4CaO4‐complexes from polar solvents acetonitrile or N, N‐dimethylformamide, which closely mimics the two water molecules on calcium ion, as well as, the oxidation states of the four manganese ions and the main geometric structure of the natural Mn4Ca‐cluster. These new artificial Mn4Ca‐complexes provide important chemical clues to understand the structure and mechanism of its biological paragon.

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