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Title: Selective, Tunable O 2 Binding in Cobalt(II)–Triazolate/Pyrazolate Metal–Organic Frameworks

Abstract

The air-free reaction of CoCl 2 with 1,3,5-tri(1H-1,2,3-triazol-5-yl)benzene (H 3 BTTri) in N,N-dimethylformamide (DMF) and methanol leads to the formation of Co-BTTri (Co 3 [(Co 4 Cl) 3 (BTTri) 8 ] 2 ·DMF), a sodalite-type metal-organic framework. Desolvation of this material generates coordinatively unsaturated low-spin cobalt(II) centers that exhibit a strong preference for binding O 2 over N 2 , with isosteric heats of adsorption (Q st ) of -34(1) and -12(1) kJ/mol, respectively. The low-spin (S = 1/2) electronic configuration of the metal centers in the desolvated framework is supported by structural, magnetic susceptibility, and computational studies. A single-crystal X-ray structure determination reveals that O 2 binds end-on to each framework cobalt center in a 1:1 ratio with a Co-O 2 bond distance of 1.973(6) Å. Replacement of one of the triazolate linkers with a more electron-donating pyrazolate group leads to the isostructural framework Co-BDTriP (Co 3 [(Co 4 Cl) 3 (BDTriP) 8 ] 2 ·DMF; H 3 BDTriP = 5,5'-(5-(1H-pyrazol-4-yl)-1,3-phenylene)bis(1H-1,2,3-triazole)), which demonstrates markedly higher yet still fully reversible O 2 affinities (Q st = -47(1) kJ/mol at low loadings). Electronic structure calculations suggest that the O 2 adducts in Co-BTTri are best described as cobalt(II)-dioxygen species with partialmore » electron transfer, while the stronger binding sites in Co-BDTriP form cobalt(III)-superoxo moieties. The stability, selectivity, and high O 2 adsorption capacity of these materials render them promising new adsorbents for air separation processes.« less

Authors:
; ; ;  [1];  [1];  [1];  [2]
  1. Department of Chemistry, and Supercomputing Institute, University of Minnesota, Minneapolis, Minnesota 55455, United States
  2. Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States
Publication Date:
Research Org.:
Univ. of California, Berkeley, CA (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Gas Separations Relevant to Clean Energy Technologies (CGS); Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Contributing Org.:
Nanoporous Materials Genome Center, funded by the U.S. Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences
OSTI Identifier:
1254878
Alternate Identifier(s):
OSTI ID: 1256715; OSTI ID: 1349938; OSTI ID: 1414760
Grant/Contract Number:  
AC02-05CH11231; AC02-06CH11357; FG02-12ER16362; SC0001015; S10-RR027172
Resource Type:
Published Article
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Name: Journal of the American Chemical Society Journal Volume: 138 Journal Issue: 22; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE

Citation Formats

Xiao, Dianne J., Gonzalez, Miguel I., Darago, Lucy E., Vogiatzis, Konstantinos D., Haldoupis, Emmanuel, Gagliardi, Laura, and Long, Jeffrey R. Selective, Tunable O 2 Binding in Cobalt(II)–Triazolate/Pyrazolate Metal–Organic Frameworks. United States: N. p., 2016. Web. doi:10.1021/jacs.6b03680.
Xiao, Dianne J., Gonzalez, Miguel I., Darago, Lucy E., Vogiatzis, Konstantinos D., Haldoupis, Emmanuel, Gagliardi, Laura, & Long, Jeffrey R. Selective, Tunable O 2 Binding in Cobalt(II)–Triazolate/Pyrazolate Metal–Organic Frameworks. United States. https://doi.org/10.1021/jacs.6b03680
Xiao, Dianne J., Gonzalez, Miguel I., Darago, Lucy E., Vogiatzis, Konstantinos D., Haldoupis, Emmanuel, Gagliardi, Laura, and Long, Jeffrey R. Thu . "Selective, Tunable O 2 Binding in Cobalt(II)–Triazolate/Pyrazolate Metal–Organic Frameworks". United States. https://doi.org/10.1021/jacs.6b03680.
@article{osti_1254878,
title = {Selective, Tunable O 2 Binding in Cobalt(II)–Triazolate/Pyrazolate Metal–Organic Frameworks},
author = {Xiao, Dianne J. and Gonzalez, Miguel I. and Darago, Lucy E. and Vogiatzis, Konstantinos D. and Haldoupis, Emmanuel and Gagliardi, Laura and Long, Jeffrey R.},
abstractNote = {The air-free reaction of CoCl 2 with 1,3,5-tri(1H-1,2,3-triazol-5-yl)benzene (H 3 BTTri) in N,N-dimethylformamide (DMF) and methanol leads to the formation of Co-BTTri (Co 3 [(Co 4 Cl) 3 (BTTri) 8 ] 2 ·DMF), a sodalite-type metal-organic framework. Desolvation of this material generates coordinatively unsaturated low-spin cobalt(II) centers that exhibit a strong preference for binding O 2 over N 2 , with isosteric heats of adsorption (Q st ) of -34(1) and -12(1) kJ/mol, respectively. The low-spin (S = 1/2) electronic configuration of the metal centers in the desolvated framework is supported by structural, magnetic susceptibility, and computational studies. A single-crystal X-ray structure determination reveals that O 2 binds end-on to each framework cobalt center in a 1:1 ratio with a Co-O 2 bond distance of 1.973(6) Å. Replacement of one of the triazolate linkers with a more electron-donating pyrazolate group leads to the isostructural framework Co-BDTriP (Co 3 [(Co 4 Cl) 3 (BDTriP) 8 ] 2 ·DMF; H 3 BDTriP = 5,5'-(5-(1H-pyrazol-4-yl)-1,3-phenylene)bis(1H-1,2,3-triazole)), which demonstrates markedly higher yet still fully reversible O 2 affinities (Q st = -47(1) kJ/mol at low loadings). Electronic structure calculations suggest that the O 2 adducts in Co-BTTri are best described as cobalt(II)-dioxygen species with partial electron transfer, while the stronger binding sites in Co-BDTriP form cobalt(III)-superoxo moieties. The stability, selectivity, and high O 2 adsorption capacity of these materials render them promising new adsorbents for air separation processes.},
doi = {10.1021/jacs.6b03680},
journal = {Journal of the American Chemical Society},
number = 22,
volume = 138,
place = {United States},
year = {Thu May 26 00:00:00 EDT 2016},
month = {Thu May 26 00:00:00 EDT 2016}
}

Journal Article:
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https://doi.org/10.1021/jacs.6b03680

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  • Wu, Jianfeng; Guo, Mei; Li, Xiao-Lei
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  • Mendiratta, Shruti; Usman, Muhammad; Chang, Chun-Chi
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  • Gonzalez, Miguel I.; Mason, Jarad A.; Bloch, Eric D.
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  • DOI: 10.1039/c7sc00449d

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  • Wu, Jianfeng; Guo, Mei; Li, Xiao-Lei
  • Chemical Communications, Vol. 54, Issue 85
  • DOI: 10.1039/c8cc06411c

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  • Shi, Yajing; Li, Na; Song, Huihua
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  • DOI: 10.1002/cjoc.201600451

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  • Zhang, Jianxin; Liu, Yuancheng; Wang, Jun
  • Journal of the Chinese Chemical Society, Vol. 65, Issue 12
  • DOI: 10.1002/jccs.201800202

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journal, September 2017

  • Reed, Douglas A.; Keitz, Benjamin K.; Oktawiec, Julia
  • Nature, Vol. 550, Issue 7674
  • DOI: 10.1038/nature23674

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  • Fathizadeh, Mahdi; Khivantsev, Konstantin; Pyrzynski, Travis J.
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  • DOI: 10.1039/c8cc01457d

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  • Melag, Leena; Sadiq, M. Munir; Smith, Stefan J. D.
  • Journal of Materials Chemistry A, Vol. 7, Issue 8
  • DOI: 10.1039/c8ta07739h

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  • Reed, Douglas A.; Xiao, Dianne J.; Jiang, Henry Z. H.
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  • DOI: 10.1039/c9sc06047b

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  • Yu, You-Zhu; Guo, Yu-Hua; Zhang, Yan-Ru
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  • DOI: 10.1039/d0cc01320j