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Title: 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) 4O 4 cubane was achieved by a simple and efficient assembly of permanganate, cobalt(II) acetate, and pyridine to form the cubane oxo cluster MnCo 3O 4(OAc) 5py 3 (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), NO 3 - (1-NO 3), and pyridine ([1-py] +). EPR spectroscopy, SQUID magnetometry, and DFT calculations thoroughly characterized the valence assignment of the cubane as [Mn IVCo III 3]. 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 MnCo 3O 4 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:
ORCiD logo [1];  [2];  [1];  [2]; ORCiD logo [1]; ORCiD logo [1];  [2];  [1]
  1. Univ. of California, Berkeley, CA (United States). Dept. of Chemistry
  2. 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) (SC-22). Chemical Sciences, Geosciences & 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:
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. 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, and Tilley, T. Don. Tue . "Manganese–Cobalt Oxido Cubanes Relevant to Manganese-Doped Water Oxidation Catalysts". United States. doi: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},
journal = {Journal of the American Chemical Society},
number = 15,
volume = 139,
place = {United States},
year = {2017},
month = {3}
}

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