A synthetic Mn4Ca-cluster mimicking the oxygen-evolving center of photosynthesis

Mimicking the oxygen evolution center Making a synthetic analog of plant photosynthesis is a key goal for exploiting solar energy and replacing fossil fuels. Zhang et al. synthesized a manganese-calcium cluster that looks and acts like the oxygen evolution center in photosystem II (see the Perspective by Sun). The mimic structurally resembles the biological complex, with the notable exception of bridging protein ligands and water-binding sites on a dangling Mn atom. Functionally, however, the cluster's metal center readily undergoes four redox transitions, which contribute to splitting water into oxygen. This and other synthetic mimics will pave the way for developing more efficient catalysts for artificial photosynthesis. Science, this issue p. 690; see also p. 635 A synthetic analog could help shed light on the molecular tools plants use to make oxygen. [Also see Perspective by Sun] Photosynthetic splitting of water into oxygen by plants, algae, and cyanobacteria is catalyzed by the oxygen-evolving center (OEC). Synthetic mimics of the OEC, which is composed of an asymmetric manganese-calcium-oxygen cluster bound to protein groups, may promote insight into the structural and chemical determinants of biological water oxidation and lead to development of superior catalysts for artificial photosynthesis. We synthesized a Mn4Ca-cluster similar to the native OEC in both the metal-oxygen core and the binding protein groups. Like the native OEC, the synthetic cluster can undergo four redox transitions and shows two magnetic resonance signals assignable to redox and structural isomerism. Comparison with previously synthesized Mn3CaO4-cubane clusters suggests that the fourth Mn ion determines redox potentials and magnetic properties of the native OEC.

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