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Title: Selective, tunable O 2 binding in cobalt(II)–triazolate/pyrazolate metal–organic frameworks

Here, the air-free reaction of CoCl 2 with 1,3,5-tri(1H- 1,2,3-triazol-5-yl)benzene (H 3BTTri) in N,N-dimethylformamide (DMF) and methanol leads to the formation of Co- BTTri (Co 3[(Co 4Cl) 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 4Cl) 3(BDTriP) 8] 2·DMF; H 3BDTriP = 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 formmore » 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] ;  [2] ;  [2] ;  [3]
  1. Univ. of California, Berkeley, CA (United States)
  2. Univ. of Minnesota, Minneapolis, MN (United States)
  3. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Publication Date:
Grant/Contract Number:
SC0001015; AC02-05CH11231; AC02-06CH11357; FG02-12ER16362; S10-RR027172
Type:
Published Article
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 138; Journal Issue: 22; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
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 Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Contributing Orgs:
Nanoporous Materials Genome Center, funded by the U.S. Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE
OSTI Identifier:
1254878
Alternate Identifier(s):
OSTI ID: 1256715; OSTI ID: 1349938; OSTI ID: 1414760

Xiao, Dianne J., Gonzalez, Miguel I., Darago, Lucy E., Vogiatzis, Konstantinos D., Haldoupis, Emmanuel, Gagliardi, Laura, and Long, Jeffrey R.. Selective, tunable O2 binding in cobalt(II)–triazolate/pyrazolate metal–organic frameworks. United States: N. p., 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 O2 binding in cobalt(II)–triazolate/pyrazolate metal–organic frameworks. United States. doi:10.1021/jacs.6b03680.
Xiao, Dianne J., Gonzalez, Miguel I., Darago, Lucy E., Vogiatzis, Konstantinos D., Haldoupis, Emmanuel, Gagliardi, Laura, and Long, Jeffrey R.. 2016. "Selective, tunable O2 binding in cobalt(II)–triazolate/pyrazolate metal–organic frameworks". United States. doi:10.1021/jacs.6b03680.
@article{osti_1254878,
title = {Selective, tunable O2 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 = {Here, the air-free reaction of CoCl2 with 1,3,5-tri(1H- 1,2,3-triazol-5-yl)benzene (H3BTTri) in N,N-dimethylformamide (DMF) and methanol leads to the formation of Co- BTTri (Co3[(Co4Cl)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 O2 over N2, with isosteric heats of adsorption (Qst) 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 O2 binds end-on to each framework cobalt center in a 1:1 ratio with a Co-O2 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 (Co3[(Co4Cl)3(BDTriP)8]2·DMF; H3BDTriP = 5,5'-(5-(1H-pyrazol-4-yl)-1,3-phenylene)bis(1H-1,2,3-triazole)), which demonstrates markedly higher yet still fully reversible O2 affinities (Qst = -47(1) kJ/mol at low loadings). Electronic structure calculations suggest that the O2 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 O2 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 = {2016},
month = {5}
}