Evidence for tetranuclear bis-μ-oxo cubane species in molecular iridium-based water oxidation catalysts from XAS analysis

The structure of a highly active pyridine-alkoxide iridium water oxidation catalyst (WOC) is examined by X-ray absorption spectroscopy (XAS). A detailed comparison with IrO 2 points to a rigid molecular unit of low nuclearity, with the best analysis suggesting a novel tetrameric iridium-oxo cubane a...

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Bibliographic Details
Published in:Chemical communications (Cambridge, England) England), 2019-07, Vol.55 (54), p.7832-7835
Main Authors: Bartlett, Stuart A, Sackville, Emma V, Gibson, Emma K, Celorrio, Veronica, Wells, Peter P, Nachtegaal, Maarten, Sheehan, Stafford W, Hintermair, Ulrich
Format: Article
Language:English
Subjects:
Catalysis
Catalysts
Cubane
Iridium
Oxidation
X ray absorption
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Summary:The structure of a highly active pyridine-alkoxide iridium water oxidation catalyst (WOC) is examined by X-ray absorption spectroscopy (XAS). A detailed comparison with IrO 2 points to a rigid molecular unit of low nuclearity, with the best analysis suggesting a novel tetrameric iridium-oxo cubane as the resting state. Latest EXAFS results suggest a 'dimer-of-dimers' as the dominant resting state of Ir-pyalk WOCs in aqueous solution.
ISSN:1359-7345
1364-548X
DOI:10.1039/c9cc02088h