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Updated: May 27, 2025

Preparation of Polyoxometalate-based Photo-responsive Membranes for the Photo-activation of Manganese Oxide Catalysts
Published on: August 7, 2018
High-Spin Manganese(V) in an Active Center Analogue of the Oxygen-Evolving Complex
Olesya S Ablyasova1,2, Mihkel Ugandi3, Esma B Boydas3
1Abteilung für Hochempfindliche Röntgenspektroskopie, Helmholtz-Zentrum Berlin für Materialien und Energie, Albert-Einstein-Straße 15, 12489 Berlin, Germany.
Abstract:
In a comprehensive investigation of the dinuclear [Mn2O3]+ cluster, the smallest dimanganese entity with two μ-oxo bridges and a terminal oxo ligand, and a simplified structural model of the active center in the oxygen-evolving complex, we identify antiferromagnetically coupled high-spin manganese centers in very different oxidation states of +2 and +5, but rule out the presence of a manganese(IV)-oxyl species by experimental X-ray absorption and X-ray magnetic circular dichroism spectroscopy combined with multireference calculations. This first identification of a high-spin manganese(V) center in any polynuclear oxidomanganese complex underscores the need for multireference computational methods to describe high-valent oxidomanganese species.
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