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Herein, we report the synthesis, characterization, crystal structure, density functional theory calculations, and water-oxidizing activity of a pivalate Mn-Ca cluster. All of the manganese atoms in the cluster are Mn(iv) ions and have a distorted MnO6 octahedral geometry. Three Mn(iv) ions together with a Ca(ii) ion and four-oxido groups form a cubic Mn3CaO4 unit which is similar to the Mn3CaO4 cluster in the water-oxidizing complex of Photosystem II. Using scanning electron microscopy, transmission electron microscopy, energy dispersive spectrometry, extended X-ray absorption spectroscopy, chronoamperometry, and electrochemical methods, a conversion into nano-sized Mn-oxide is observed for the cluster in the water-oxidation reaction.

A synthetic manganese–calcium cluster similar to the catalyst of Photosystem II: challenges for biomimetic water oxidation