The synthesis of a novel class of reactive Mn-Ca-oxo clusters, as structural models of the oxygen-evolving complex of photosystem II, has been achieved through self-assembly with substituted pyridyl ligands. A range of metallo-core stiochiometries (MnII4, MnII3Ca, MnII5Ca, MnII4Ca2, and MnII3Ca4) features a hemicubane motif with central/internal Ca atoms with labile THF-solvent coordination. The hemicubane geometry features apical MnII metallo-sites bridged by core oxygen atoms, resembling the pendant Mn-oxo feature of the OEC. The redox activity of this class of biomimcs has been investigated in organic solvent, including propylene carbonate. Propylene carbonate decomposes in the presence of water at a potential of 2V. The heterometallic hemicubanes, MnII3Ca, MnII5Ca, MnII4Ca2, and MnII3Ca4, are capable of catalyzing the decomposition pathway, and the stoichiometry most reminiscent of the native OEC active site, MnII3Ca, is the most reactive. Implications for biological water oxidation will be discussed.

Preparation of reactive biomimics of the oxygen-evolving complex

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

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