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Manganese–Cobalt Oxido Cubanes Relevant to Manganese-Doped Water Oxidation Catalysts
Abstract
Incorporation of Mn into an established water oxidation catalyst based on a Co(III)4O4 cubane was achieved by a simple and efficient assembly of permanganate, cobalt(II) acetate, and pyridine to form the cubane oxo cluster MnCo3O4(OAc)5py3 (OAc = acetate, py = pyridine) (1-OAc) in good yield. This allows characterization of electronic and chemical properties for a manganese center in a cobalt oxide environment, and provides a molecular model for Mn-doped cobalt oxides. The electronic properties of the cubane are readily tuned by exchange of the OAc- ligand for Cl- (1-Cl), NO3- (1-NO3), and pyridine ([1-py]+). EPR spectroscopy, SQUID magnetometry, and DFT calculations thoroughly characterized the valence assignment of the cubane as [MnIVCoIII3]. These cubanes are redox-active, and calculations reveal that the Co ions behave as the reservoir for electrons, but their redox potentials are tuned by the choice of ligand at Mn. This MnCo3O4 cubane system represents a new class of easily prepared, versatile, and redox-active oxido clusters that should contribute to an understanding of mixed-metal, Mn-containing oxides.
- Authors:
-
[1];
[1];
[1];
- Univ. of California, Berkeley, CA (United States). Dept. of Chemistry
- Univ. of California, Davis, CA (United States). Dept. of Chemistry
- Publication Date:
- Research Org.:
- Univ. of California, Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division; National Science Foundation (NSF); National Institutes of Health (NIH)
- OSTI Identifier:
- 1469819
- Grant/Contract Number:
- AC02-05CH11231; FG02-11ER16282; S10-RR027172
- Resource Type:
- Journal Article: Accepted Manuscript
- Journal Name:
- Journal of the American Chemical Society
- Additional Journal Information:
- Journal Volume: 139; Journal Issue: 15; Journal ID: ISSN 0002-7863
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Nguyen, Andy I., Suess, Daniel L. M., Darago, Lucy E., Oyala, Paul H., Levine, Daniel S., Ziegler, Micah S., Britt, R. David, and Tilley, T. Don. Manganese–Cobalt Oxido Cubanes Relevant to Manganese-Doped Water Oxidation Catalysts. United States: N. p., 2017.
Web. doi:10.1021/jacs.7b01792.
Nguyen, Andy I., Suess, Daniel L. M., Darago, Lucy E., Oyala, Paul H., Levine, Daniel S., Ziegler, Micah S., Britt, R. David, & Tilley, T. Don. Manganese–Cobalt Oxido Cubanes Relevant to Manganese-Doped Water Oxidation Catalysts. United States. https://doi.org/10.1021/jacs.7b01792
Nguyen, Andy I., Suess, Daniel L. M., Darago, Lucy E., Oyala, Paul H., Levine, Daniel S., Ziegler, Micah S., Britt, R. David, and Tilley, T. Don. 2017.
"Manganese–Cobalt Oxido Cubanes Relevant to Manganese-Doped Water Oxidation Catalysts". United States. https://doi.org/10.1021/jacs.7b01792. https://www.osti.gov/servlets/purl/1469819.
@article{osti_1469819,
title = {Manganese–Cobalt Oxido Cubanes Relevant to Manganese-Doped Water Oxidation Catalysts},
author = {Nguyen, Andy I. and Suess, Daniel L. M. and Darago, Lucy E. and Oyala, Paul H. and Levine, Daniel S. and Ziegler, Micah S. and Britt, R. David and Tilley, T. Don},
abstractNote = {Incorporation of Mn into an established water oxidation catalyst based on a Co(III)4O4 cubane was achieved by a simple and efficient assembly of permanganate, cobalt(II) acetate, and pyridine to form the cubane oxo cluster MnCo3O4(OAc)5py3 (OAc = acetate, py = pyridine) (1-OAc) in good yield. This allows characterization of electronic and chemical properties for a manganese center in a cobalt oxide environment, and provides a molecular model for Mn-doped cobalt oxides. The electronic properties of the cubane are readily tuned by exchange of the OAc- ligand for Cl- (1-Cl), NO3- (1-NO3), and pyridine ([1-py]+). EPR spectroscopy, SQUID magnetometry, and DFT calculations thoroughly characterized the valence assignment of the cubane as [MnIVCoIII3]. These cubanes are redox-active, and calculations reveal that the Co ions behave as the reservoir for electrons, but their redox potentials are tuned by the choice of ligand at Mn. This MnCo3O4 cubane system represents a new class of easily prepared, versatile, and redox-active oxido clusters that should contribute to an understanding of mixed-metal, Mn-containing oxides.},
doi = {10.1021/jacs.7b01792},
url = {https://www.osti.gov/biblio/1469819},
journal = {Journal of the American Chemical Society},
issn = {0002-7863},
number = 15,
volume = 139,
place = {United States},
year = {Tue Mar 28 00:00:00 EDT 2017},
month = {Tue Mar 28 00:00:00 EDT 2017}
}
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Figures / Tables:
Figure 1: Comparison of models for cobalt oxyhydroxide and manganese-doped-cobalt oxyhydroxide.
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