Heuristic rules that allow identifying the preferred mixed-valence isomers and Jahn-Teller axis arrangements in the water oxidation catalyst [(Mn O )(V O )(OAc) ] and its activated form [(Mn O )(V O )(OAc) (H O)(OH)] are derived. These rules are based on computing all combinatorially possible mixed-valence isomers and Jahn-Teller axis arrangements of the Mn atoms, and associate energetic costs with some structural features, like crossings of multiple Jahn-Teller axes, the location of these axes, or the involved ligands. It is found that the different oxidation states localize on different Mn centers, giving rise to clear Jahn-Teller distortions, unlike in previous crystallographic findings where an apparent valence delocalization was found.
View Article and Find Full Text PDFWe report IR and UV/Vis spectroscopic signatures that allow discriminating between the oxidation states of the manganese-based water oxidation catalyst [(Mn O )(V O )(OAc) ] . Simulated IR spectra show that V=O stretching vibrations in the 900-1000 cm region shift consistently by about 20 cm per oxidation equivalent. Multiple bands in the 1450-1550 cm region also change systematically upon oxidation/reduction.
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