Rare-Earth Elements Can Structurally and Energetically Replace the Calcium in a Synthetic Mn₄CaO₄-Cluster Mimicking...

The oxygen-evolving center (OEC) in photosynthesis is a unique biological Mn₄CaO₅ cluster catalyzing the water-splitting reaction. A great current challenge is to achieve a robust and precise mimic of the OEC in the laboratory. Herein, we report synthetic Mn₄XO₄ clusters (X = calcium, yttrium, gadolinium) that closely resemble the OEC with regard to the main metal-oxide core and peripheral ligands, as well as the oxidation states of the four Mn ions and the redox potential of the cluster. We demonstrate that rare-earth elements can structurally replace the calcium in neutral Mn₄XO₄ clusters. All three Mn₄XO₄ clusters with different redox-inactive metal ions display essentially the same redox properties, challenging the conventional view that the Lewis acidity of the redox-inactive metal ions could modulate the redox potential of the heteronuclear-oxide clusters. The new synthetic rare-earth element-containing Mn₄XO₄ clusters reported here provide robust and structurally well-defined chemical models and shed new light on the design of new water-splitting catalysts in artificial photosynthesis.