Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 137, Issue 34, Pages 11076-11084Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jacs.5b05831
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Funding
- Swiss National Science Foundation (Sinergia) [CRSII2_136205/1]
- University Research Priority Program (URPP) for solar light to chemical energy conversion (LightChEC)
- National Center of Competence in Research Materials Revolution: Computational Design and Discovery of Novel Materials (NCCR-MARVEL)
- Swiss National Science Foundation (SNF) [CRSII2_136205] Funding Source: Swiss National Science Foundation (SNF)
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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 [Co(3)(II)Ln(hmp)(4)(OAc)(5)H2O] ({Co(3)(II)Ln(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 {Co(3)(II)Ln(OR)(4)} cubanes promote bioinspired WOC design by newly combining Ln(3+) 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 {Co(3)(II)Ln(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 Ln(3+) centers is linked to favorable ligand mobility, and the experimental trends are substantiated with Born-Oppenheimer molecular dynamics studies.
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