Rare-Earth Elements Can Structurally and Energetically Replace the Calcium in a Synthetic Mn4CaO4-Cluster Mimicking the Oxygen-Evolving Center in Photosynthesis

Heteronuclear molecule Rare-earth element
DOI: 10.1021/jacs.1c09085 Publication Date: 2021-10-14T06:18:06Z
ABSTRACT
The oxygen-evolving center (OEC) in photosynthesis is a unique biological Mn4CaO5 cluster catalyzing the water-splitting reaction. A great current challenge to achieve robust and precise mimic of OEC laboratory. Herein, we report synthetic Mn4XO4 clusters (X = calcium, yttrium, gadolinium) that closely resemble with regard main metal-oxide core peripheral ligands, as well oxidation states four Mn ions redox potential cluster. We demonstrate rare-earth elements can structurally replace calcium neutral clusters. All three different redox-inactive metal display essentially same properties, challenging conventional view Lewis acidity could modulate heteronuclear-oxide new element-containing reported here provide well-defined chemical models shed light on design catalysts artificial photosynthesis.
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