Abstract

The oxygen-evolving center (OEC) in photosystem II (PSII) of plants, algae and cyanobacteria is a unique biocatalyst that splits water into electrons, protons and dioxygen. The crystallographic studies of PSII have revealed that the OEC is composed of a Mn3CaO4 cubane attached by a dangling Mn ion, forming an asymmetric Mn4CaO5-cluster. A long-standing goal in science seeks to understand the structure-function relationship of the OEC and develop man-made catalysts for the highly efficient water-splitting reaction in artificial photosynthesis. It is of a great challenge for chemists to synthesize the OEC in the laboratory. Significant advances have been achieved recently. We have reported the first artificial Mn4CaO4-cluster that closely mimics both the geometric and electronic structures of the OEC in PSII, providing a structurally well-defined chemical model to investigate the structure-function relationship of the natural Mn4CaO5-cluster. The detailed investigations on this artificial Mn4CaO4-cluster would shed new insights into the mechanism of the oxygen-evolution reaction in natural photosynthesis and the development of efficient catalysts for the water-splitting reaction in artificial photosynthesis.

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