Synthetic Mn₃Ce₂O₅-Cluster Mimicking the Oxygen-Evolving Center in Photosynthesis

The photosynthetic oxygen-evolving center (OEC) is a unique Mn₄CaO₅-cluster that catalyses water splitting into electrons, protons, and dioxygen. Precisely structural and functional mimicking of the OEC is a long-standing challenge and pressingly needed for understanding the structure-function relationship and catalytic mechanism of O-O bond formation. Herein we report two simple and robust artificial Mn₃Ce₂O₅-complexes that display a remarkable structural similarity to the OEC in regarding of the ten-atom core (five metal ions and five oxygen bridges) and the alkyl carboxylate peripheral ligands. This Mn₃Ce₂O₅-cluster can catalyse the water-splitting reaction on the surface of ITO electrode. These results clearly show that cerium can structurally and functionally replace both calcium and manganese in the cluster. Mass spectroscopic measurements demonstrate that the oxide bridges in the cluster are exchangeable and can be rapidly replaced by the isotopic oxygen of H₂ ¹⁸O in acetonitrile solution, which supports that the oxide bridge(s) may serve as the active site for the formation of O-O bond during the water-splitting reaction. These results would contribute to our understanding of the structure-reactivity relationship of both natural and artificial clusters and shed new light on the development of efficient water-splitting catalysts in artificial photosynthesis.