Reversible O–O Bond Scission and O2 Evolution at MOF-Supported Tetramanganese Clusters
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Author(s)
He, Xin
Iliescu, Andrei
Yang, Tzuhsiung
Arguilla, Maxx Q
Chen, Tianyang
Kulik, Heather J
Dincă, Mircea
Date Issued
July 20, 2023
Journal
Journal of the American Chemical Society
Publisher
American Chemical Society
Citation
Reversible O–O Bond Scission and O2 Evolution at MOF-Supported Tetramanganese Clusters. Xin He, Andrei Iliescu, Tzuhsiung Yang, Maxx Q. Arguilla, Tianyang Chen, Heather J. Kulik, and Mircea Dincă
Journal of the American Chemical Society 2023 145 (30), 16872-16878.
Version
Author's final manuscript
Abstract
The scission of the O–O bond in O2 during respiration and the formation of the O–O bond during photosynthesis are the engines of aerobic life. Likewise, the reduction of O2 and the oxidation of reduced oxygen species to form O2 are indispensable components for emerging renewable technologies, including energy storage and conversion, yet discrete molecule-like systems that promote these fundamental reactions are rare. Herein, we report a square-planar tetramanganese cluster formed by self-assembly within a metal–organic framework that reversibly reduces O2 by four electrons, facilitating the interconversion between molecular O2 and metal-oxo species. The tetranuclear cluster spontaneously cleaves the O–O bond of O2 at room temperature to generate a tetramanganese-bis(μ2-oxo) species, which, in turn, is competent for O–O bond reformation and O2 evolution at elevated temperatures, enabled by the head-to-head orientation of two oxo species. This study demonstrates the viability of four-electron interconversion between molecular O2 and metal-oxo species and highlights the importance of site isolation for achieving multi-electron chemistry at polynuclear metal clusters.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
Massachusetts Institute of Technology. Department of Chemical Engineering
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DOI of Published Version
https://doi.org/10.1021/jacs.3c05374
