Journal
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
Volume 110, Issue 25, Pages 10084-10088Publisher
NATL ACAD SCIENCES
DOI: 10.1073/pnas.1302677110
Keywords
electrochemistry; heterometallic complexes; manganese clusters; model complexes; photosynthesis
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Funding
- California Institute of Technology
- Searle Scholars Program
- National Science Foundation (NSF) CAREER [CHE-1151918]
- Sandia Campus Executive Fellowship
- NSF Chemistry Research Instrumentation award [CHE-0639094]
- Direct For Mathematical & Physical Scien
- Division Of Chemistry [1151918] Funding Source: National Science Foundation
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Understanding the effect of redox-inactive metals on the properties of biological and heterogeneous water oxidation catalysts is important both fundamentally and for improvement of future catalyst designs. In this work, heterometallic manganese-oxido cubane clusters [MMn3O4] (M = Sr2+, Zn2+, Sc3+, Y3+) structurally relevant to the oxygen-evolving complex (OEC) of photosystem II were prepared and characterized. The reduction potentials of these clusters and other related mixed metal manganese-tetraoxido complexes are correlated with the Lewis acidity of the apical redox-inactive metal in a manner similar to a related series of heterometallic manganese-dioxido clusters. The redox potentials of the [SrMn3O4] and [CaMn3O4] clusters are close, which is consistent with the observation that the OEC is functional only with one of these two metals. Considering our previous studies of [MMn3O2] moieties, the present results with more structurally accurate models of the OEC ([MMn3O4]) suggest a general relationship between the reduction potentials of heterometallic oxido clusters and the Lewis acidities of incorporated cations that applies to diverse structural motifs. These findings support proposals that one function of calcium in the OEC is to modulate the reduction potential of the cluster to allow electron transfer.
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