Abstract

A virtually identical cubical or cubane core structure appears to be a key commonality in several active homogeneous, heterogeneous and enzymatic water oxidation catalysts. We show that X-ray crystal structures of the CaMn3O4 core of the water oxidizing complex of Photosystem II coincide remarkably closely with comparable structures in a range of non-biological Co or Mn-based homogeneous and heterogeneous water oxidation catalysts. Included amongst these are molecular Co4O4 and Mn4O4 cubanes, as well as Co and Mn spinels containing cubical arrangements. This observation supports the existence of an optimum structural element for water oxidation catalysis. It also offers a potential avenue for comparing and relating homogeneous, heterogeneous and enzymatic catalysis to each other.

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