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 »
- Authors:
-
- Department of Chemistry, and Supercomputing Institute, University of Minnesota, Minneapolis, Minnesota 55455, United States
- 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}
}
https://doi.org/10.1021/jacs.6b03680
Web of Science
Works referencing / citing this record:
CCDC 1495151: Experimental Crystal Structure Determination: AQOKUO : cobalt(ii) (5,5'-[5-(pyrazol-1-id-4-yl)-1,3-phenylene]bis(1,2,3-triazol-1-ide)) chloride dioxygen
dataset, July 2016
- Xiao, Dianne; Gonzalez, Miguel; Darago, Lucy
- Cambridge Structural Database (CSD)
CCDC 1495152: Experimental Crystal Structure Determination: AQOLAV : cobalt(ii) (5,5'-[5-(pyrazol-1-id-4-yl)-1,3-phenylene]bis(1,2,3-triazol-1-ide)) chloride dioxygen
dataset, July 2016
- Xiao, Dianne; Gonzalez, Miguel; Darago, Lucy
- Cambridge Structural Database (CSD)
CCDC 1495153: Experimental Crystal Structure Determination: AQOLEZ : catena-[sesquikis(cobalt) octakis(μ-4,4'-[5-(1H-pyrazol-4-yl)-1,3-phenylene]bis(1H-1,2,3-triazole))-tris(μ-chloro)-dodecakis(methanol)-dodeca-cobalt]
dataset, July 2016
- Xiao, Dianne; Gonzalez, Miguel; Darago, Lucy
- Cambridge Structural Database (CSD)
CCDC 1495154: Experimental Crystal Structure Determination: AQOLID : catena-[sesqui-cobalt octakis(μ-5,5',5''-(benzene-1,3,5-triyl)tris(1H-1,2,3-triazole))-tris(μ-chloro)-dodeca-cobalt dioxygen unknown solvate]
dataset, July 2016
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Space Group: P m 3 m (221), Cell: a 18.7940(7)Å b 18.7940(7)Å c 18.7940(7)Å, α 90° β 90° γ 90°
dataset, July 2016
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Space Group: P m 3 m (221), Cell: a 18.8345(7)Å b 18.8345(7)Å c 18.8345(7)Å, α 90° β 90° γ 90°
dataset, July 2016
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dataset, July 2016
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