Manganese–Cobalt Oxido Cubanes Relevant to Manganese-Doped Water Oxidation Catalysts

doi:10.1021/jacs.7b01792

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:

^[1]; Suess, Daniel L. M. ^[2]; Darago, Lucy E. ^[1]; Oyala, Paul H. ^[2];

^[1];

^[1]; Britt, R. David ^[2]; Tilley, T. Don ^[1]

Univ. of California, Berkeley, CA (United States). Dept. of Chemistry
Univ. of California, Davis, CA (United States). Dept. of Chemistry

Publication Date:: 2017-03-28

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.

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                    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.

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                    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.

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@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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DOI: 10.1021/jacs.7b01792

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Cited by: 13 works

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Figure 1: Comparison of models for cobalt oxyhydroxide and manganese-doped-cobalt oxyhydroxide.

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Works referencing / citing this record:

CCDC 1566348: Experimental Crystal Structure Determination: GEBWIW : tetrakis(μ-acetato)-tetrakis(μ-oxo)-acetato-tris(pyridine)-tri-cobalt-manganese dichloromethane solvate
dataset, August 2017

Nguyen, Andy I.; Suess, Daniel L. M.; Darago, Lucy E.
Cambridge Structural Database (CSD)
DOI: 10.5517/ccdc.csd.cc1pkxcj

CCDC 1566349: Experimental Crystal Structure Determination: GEBWOC : tetrakis(μ-acetato)-tetrakis(μ-oxo)-tris(pyridine)-(p-toluenesulfonato)-tri-cobalt-manganese acetonitrile solvate
dataset, August 2017

Nguyen, Andy I.; Suess, Daniel L. M.; Darago, Lucy E.
Cambridge Structural Database (CSD)
DOI: 10.5517/ccdc.csd.cc1pkxdk

CCDC 1566350: Experimental Crystal Structure Determination: GEBWUI : tetrakis(μ-acetato)-tetrakis(μ-oxo)-tetrakis(pyridine)-tri-cobalt-manganese hexafluorophosphate dichloromethane solvate
dataset, August 2017

Nguyen, Andy I.; Suess, Daniel L. M.; Darago, Lucy E.
Cambridge Structural Database (CSD)
DOI: 10.5517/ccdc.csd.cc1pkxfl

CCDC 1566352: Experimental Crystal Structure Determination: GEBXET : tetrakis(μ-oxo)-tetrakis(μ-acetato)-(nitrato)-tris(pyridine)-tri-cobalt-manganese dichloromethane solvate
dataset, August 2017

Nguyen, Andy; Suess, Daniel; Darago, Lucy
Cambridge Structural Database (CSD)
DOI: 10.5517/ccdc.csd.cc1pkxhn

CCDC 1566351: Experimental Crystal Structure Determination: GEBXAP : tetrakis(μ-aetato)-tetrakis(μ-oxo)-chloro-tris(pyridine)-tri-cobalt-manganese dichloromethane solvate
dataset, August 2017

Nguyen, Andy I.; Suess, Daniel L. M.; Darago, Lucy E.
Cambridge Structural Database (CSD)
DOI: 10.5517/ccdc.csd.cc1pkxgm

Half-sandwich Ir (III) and Rh (III) complexes as catalysts for water oxidation with double-site: Half-sandwich catalysts for water oxidation
journal, June 2019

Li, Peng; Liu, Jin-Bao; Han, Sheng
Applied Organometallic Chemistry
DOI: 10.1002/aoc.5040

Smoothing the single-crystal to single-crystal conversions of a two-dimensional metal–organic framework via the hetero-metal doping of the linear trimetallic secondary building unit
journal, January 2018

Chao, Meng-Yao; Chen, Jing; Young, David J.
Dalton Transactions, Vol. 47, Issue 38
DOI: 10.1039/c8dt02813c

Heterometallic mixed-valence complex with a {Co ^II Co ^III Cu ₂ O ₄ } core as a new type of cobalt-based oxide cubane
journal, January 2018

Stetsiuk, Oleh; El-Ghayoury, Abdelkrim; Kokozay, Vladimir N.
Journal of Coordination Chemistry, Vol. 71, Issue 1
DOI: 10.1080/00958972.2018.1425406

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Title: Manganese–Cobalt Oxido Cubanes Relevant to Manganese-Doped Water Oxidation Catalysts

Abstract

Citation Formats

Figures / Tables:

CCDC 1566348: Experimental Crystal Structure Determination: GEBWIW : tetrakis(μ-acetato)-tetrakis(μ-oxo)-acetato-tris(pyridine)-tri-cobalt-manganese dichloromethane solvate dataset, August 2017

CCDC 1566349: Experimental Crystal Structure Determination: GEBWOC : tetrakis(μ-acetato)-tetrakis(μ-oxo)-tris(pyridine)-(p-toluenesulfonato)-tri-cobalt-manganese acetonitrile solvate dataset, August 2017

CCDC 1566350: Experimental Crystal Structure Determination: GEBWUI : tetrakis(μ-acetato)-tetrakis(μ-oxo)-tetrakis(pyridine)-tri-cobalt-manganese hexafluorophosphate dichloromethane solvate dataset, August 2017

CCDC 1566352: Experimental Crystal Structure Determination: GEBXET : tetrakis(μ-oxo)-tetrakis(μ-acetato)-(nitrato)-tris(pyridine)-tri-cobalt-manganese dichloromethane solvate dataset, August 2017

CCDC 1566351: Experimental Crystal Structure Determination: GEBXAP : tetrakis(μ-aetato)-tetrakis(μ-oxo)-chloro-tris(pyridine)-tri-cobalt-manganese dichloromethane solvate dataset, August 2017

Half-sandwich Ir (III) and Rh (III) complexes as catalysts for water oxidation with double-site: Half-sandwich catalysts for water oxidation journal, June 2019

Smoothing the single-crystal to single-crystal conversions of a two-dimensional metal–organic framework via the hetero-metal doping of the linear trimetallic secondary building unit journal, January 2018

Heterometallic mixed-valence complex with a {Co II Co III Cu 2 O 4 } core as a new type of cobalt-based oxide cubane journal, January 2018

CCDC 1566348: Experimental Crystal Structure Determination: GEBWIW : tetrakis(μ-acetato)-tetrakis(μ-oxo)-acetato-tris(pyridine)-tri-cobalt-manganese dichloromethane solvate
dataset, August 2017

CCDC 1566349: Experimental Crystal Structure Determination: GEBWOC : tetrakis(μ-acetato)-tetrakis(μ-oxo)-tris(pyridine)-(p-toluenesulfonato)-tri-cobalt-manganese acetonitrile solvate
dataset, August 2017

CCDC 1566350: Experimental Crystal Structure Determination: GEBWUI : tetrakis(μ-acetato)-tetrakis(μ-oxo)-tetrakis(pyridine)-tri-cobalt-manganese hexafluorophosphate dichloromethane solvate
dataset, August 2017

CCDC 1566352: Experimental Crystal Structure Determination: GEBXET : tetrakis(μ-oxo)-tetrakis(μ-acetato)-(nitrato)-tris(pyridine)-tri-cobalt-manganese dichloromethane solvate
dataset, August 2017

CCDC 1566351: Experimental Crystal Structure Determination: GEBXAP : tetrakis(μ-aetato)-tetrakis(μ-oxo)-chloro-tris(pyridine)-tri-cobalt-manganese dichloromethane solvate
dataset, August 2017

Half-sandwich Ir (III) and Rh (III) complexes as catalysts for water oxidation with double-site: Half-sandwich catalysts for water oxidation
journal, June 2019

Smoothing the single-crystal to single-crystal conversions of a two-dimensional metal–organic framework via the hetero-metal doping of the linear trimetallic secondary building unit
journal, January 2018

Heterometallic mixed-valence complex with a {Co ^II Co ^III Cu ₂ O ₄ } core as a new type of cobalt-based oxide cubane
journal, January 2018