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3d–4f {CoII3Ln(OR)4} Cubanes as Bio-Inspired Water Oxidation Catalysts


Evangelisti, Fabio; Moré, René; Hodel, Florian; Luber, Sandra; Patzke, Greta R (2015). 3d–4f {CoII3Ln(OR)4} Cubanes as Bio-Inspired Water Oxidation Catalysts. Journal of the American Chemical Society, 137(34):11076-11084.

Abstract

Although the {CaMn4O5} oxygen evolving complex (OEC) of photosystem II is a major paradigm for water oxidation catalyst (WOC) development, the comprehensive translation of its key features into active molecular WOCs remains challenging. The [CoII3Ln(hmp)4(OAc)5H2O] ({CoII3Ln(OR)4}; Ln = Ho–Yb, hmp = 2-(hydroxymethyl)pyridine) cubane WOC series is introduced as a new springboard to address crucial design parameters, ranging from nuclearity and redox-inactive promoters to operational stability and ligand exchange properties. The {CoII3Ln(OR)4} cubanes promote bioinspired WOC design by newly combining Ln3+ centers as redox-inactive Ca2+ analogues with flexible aqua-/acetate ligands into active and stable WOCs (max. TON/TOF values of 211/9 s–1). Furthermore, they open up the important family of 3d–4f complexes for photocatalytic applications. The stability of the {CoII3Ln(OR)4} WOCs under photocatalytic conditions is demonstrated with a comprehensive analytical strategy including trace metal analyses and solution-based X-ray absorption spectroscopy (XAS) investigations. The productive influence of the Ln3+ centers is linked to favorable ligand mobility, and the experimental trends are substantiated with Born–Oppenheimer molecular dynamics studies.

Abstract

Although the {CaMn4O5} oxygen evolving complex (OEC) of photosystem II is a major paradigm for water oxidation catalyst (WOC) development, the comprehensive translation of its key features into active molecular WOCs remains challenging. The [CoII3Ln(hmp)4(OAc)5H2O] ({CoII3Ln(OR)4}; Ln = Ho–Yb, hmp = 2-(hydroxymethyl)pyridine) cubane WOC series is introduced as a new springboard to address crucial design parameters, ranging from nuclearity and redox-inactive promoters to operational stability and ligand exchange properties. The {CoII3Ln(OR)4} cubanes promote bioinspired WOC design by newly combining Ln3+ centers as redox-inactive Ca2+ analogues with flexible aqua-/acetate ligands into active and stable WOCs (max. TON/TOF values of 211/9 s–1). Furthermore, they open up the important family of 3d–4f complexes for photocatalytic applications. The stability of the {CoII3Ln(OR)4} WOCs under photocatalytic conditions is demonstrated with a comprehensive analytical strategy including trace metal analyses and solution-based X-ray absorption spectroscopy (XAS) investigations. The productive influence of the Ln3+ centers is linked to favorable ligand mobility, and the experimental trends are substantiated with Born–Oppenheimer molecular dynamics studies.

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Additional indexing

Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
08 University Research Priority Programs > Solar Light to Chemical Energy Conversion
Dewey Decimal Classification:540 Chemistry
Language:English
Date:2 September 2015
Deposited On:13 Jan 2016 16:01
Last Modified:05 Apr 2016 19:52
Publisher:American Chemical Society (ACS)
ISSN:0002-7863
Publisher DOI:https://doi.org/10.1021/jacs.5b05831

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