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Title: Structural characterization of framework–gas interactions in the metal–organic framework Co 2 (dobdc) by in situ single-crystal X-ray diffraction

Abstract

The crystallographic characterization of framework–guest interactions in metal–organic frameworks allows the location of guest binding sites and provides meaningful information on the nature of these interactions, enabling the correlation of structure with adsorption behavior. Here, techniques developed for in situ single-crystal X-ray diffraction experiments on porous crystals have enabled the direct observation of CO, CH 4, N 2, O 2, Ar, and P 4 adsorption in Co2(dobdc) (dobdc 4– = 2,5-dioxido-1,4-benzenedicarboxylate), a metal–organic framework bearing coordinatively unsaturated cobalt(II) sites. All these molecules exhibit such weak interactions with the high-spin cobalt(II) sites in the framework that no analogous molecular structures exist, demonstrating the utility of metal–organic frameworks as crystalline matrices for the isolation and structural determination of unstable species. Notably, the Co–CH 4 and Co–Ar interactions observed in Co 2(dobdc) represent, to the best of our knowledge, the first single-crystal structure determination of a metal–CH 4 interaction and the first crystallographically characterized metal–Ar interaction. Analysis of low-pressure gas adsorption isotherms confirms that these gases exhibit mainly physisorptive interactions with the cobalt(II) sites in Co 2(dobdc), with differential enthalpies of adsorption as weak as –17(1) kJ mol –1 (for Ar). Moreover, the structures of Co 2(dobdc)·3.8N 2, Co 2(dobdc)·5.9O 2, and Comore » 2(dobdc)·2.0Ar reveal the location of secondary (N 2, O 2, and Ar) and tertiary (O 2) binding sites in Co 2(dobdc), while high-pressure CO 2, CO, CH 4, N 2, and Ar adsorption isotherms show that these binding sites become more relevant at elevated pressures.« less

Authors:
ORCiD logo [1];  [1];  [1];  [2];  [2];  [2]; ORCiD logo [3]; ORCiD logo [4]
  1. Univ. of California, Berkeley, CA (United States)
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Ecole Polytechnique Federale de Lausanne (EPFL), Sion (Switzerland)
  4. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1379647
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Chemical Science
Additional Journal Information:
Journal Volume: 8; Journal Issue: 6; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Gonzalez, Miguel I., Mason, Jarad A., Bloch, Eric D., Teat, Simon J., Gagnon, Kevin J., Morrison, Gregory Y., Queen, Wendy L., and Long, Jeffrey R. Structural characterization of framework–gas interactions in the metal–organic framework Co2 (dobdc) by in situ single-crystal X-ray diffraction. United States: N. p., 2017. Web. doi:10.1039/c7sc00449d.
Gonzalez, Miguel I., Mason, Jarad A., Bloch, Eric D., Teat, Simon J., Gagnon, Kevin J., Morrison, Gregory Y., Queen, Wendy L., & Long, Jeffrey R. Structural characterization of framework–gas interactions in the metal–organic framework Co2 (dobdc) by in situ single-crystal X-ray diffraction. United States. doi:10.1039/c7sc00449d.
Gonzalez, Miguel I., Mason, Jarad A., Bloch, Eric D., Teat, Simon J., Gagnon, Kevin J., Morrison, Gregory Y., Queen, Wendy L., and Long, Jeffrey R. Wed . "Structural characterization of framework–gas interactions in the metal–organic framework Co2 (dobdc) by in situ single-crystal X-ray diffraction". United States. doi:10.1039/c7sc00449d. https://www.osti.gov/servlets/purl/1379647.
@article{osti_1379647,
title = {Structural characterization of framework–gas interactions in the metal–organic framework Co2 (dobdc) by in situ single-crystal X-ray diffraction},
author = {Gonzalez, Miguel I. and Mason, Jarad A. and Bloch, Eric D. and Teat, Simon J. and Gagnon, Kevin J. and Morrison, Gregory Y. and Queen, Wendy L. and Long, Jeffrey R.},
abstractNote = {The crystallographic characterization of framework–guest interactions in metal–organic frameworks allows the location of guest binding sites and provides meaningful information on the nature of these interactions, enabling the correlation of structure with adsorption behavior. Here, techniques developed for in situ single-crystal X-ray diffraction experiments on porous crystals have enabled the direct observation of CO, CH4, N2, O2, Ar, and P4 adsorption in Co2(dobdc) (dobdc4– = 2,5-dioxido-1,4-benzenedicarboxylate), a metal–organic framework bearing coordinatively unsaturated cobalt(II) sites. All these molecules exhibit such weak interactions with the high-spin cobalt(II) sites in the framework that no analogous molecular structures exist, demonstrating the utility of metal–organic frameworks as crystalline matrices for the isolation and structural determination of unstable species. Notably, the Co–CH4 and Co–Ar interactions observed in Co2(dobdc) represent, to the best of our knowledge, the first single-crystal structure determination of a metal–CH4 interaction and the first crystallographically characterized metal–Ar interaction. Analysis of low-pressure gas adsorption isotherms confirms that these gases exhibit mainly physisorptive interactions with the cobalt(II) sites in Co2(dobdc), with differential enthalpies of adsorption as weak as –17(1) kJ mol–1 (for Ar). Moreover, the structures of Co2(dobdc)·3.8N2, Co2(dobdc)·5.9O2, and Co2(dobdc)·2.0Ar reveal the location of secondary (N2, O2, and Ar) and tertiary (O2) binding sites in Co2(dobdc), while high-pressure CO2, CO, CH4, N2, and Ar adsorption isotherms show that these binding sites become more relevant at elevated pressures.},
doi = {10.1039/c7sc00449d},
journal = {Chemical Science},
number = 6,
volume = 8,
place = {United States},
year = {Wed Apr 19 00:00:00 EDT 2017},
month = {Wed Apr 19 00:00:00 EDT 2017}
}

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Works referenced in this record:

Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides
journal, September 1976


An In Situ High-Temperature Single-Crystal Investigation of a Dehydrated Metal-Organic Framework Compound and Field-Induced Magnetization of One-Dimensional Metal-Oxygen Chains
journal, October 2005

  • Dietzel, Pascal D. C.; Morita, Yusuke; Blom, Richard
  • Angewandte Chemie International Edition, Vol. 44, Issue 39, p. 6354-6358
  • DOI: 10.1002/anie.200501508

Small-Molecule Adsorption in Open-Site Metal–Organic Frameworks: A Systematic Density Functional Theory Study for Rational Design
journal, January 2015

  • Lee, Kyuho; Howe, Joshua D.; Lin, Li-Chiang
  • Chemistry of Materials, Vol. 27, Issue 3, p. 668-678
  • DOI: 10.1021/cm502760q

Gas Adsorption Sites in a Large-Pore Metal-Organic Framework
journal, August 2005

  • Rowsell, Jesse L. C.; Spencer, Elinor C.; Eckert, Juergen
  • Science, Vol. 309, Issue 5739, p. 1350-1354
  • DOI: 10.1126/science.1113247

Hydrogen storage in metal–organic frameworks
journal, January 2009

  • Murray, Leslie J.; Dincă, Mircea; Long, Jeffrey R.
  • Chemical Society Reviews, Vol. 38, Issue 5, p. 1294-1314
  • DOI: 10.1039/b802256a

Dramatic Tuning of Carbon Dioxide Uptake via Metal Substitution in a Coordination Polymer with Cylindrical Pores
journal, August 2008

  • Caskey, Stephen R.; Wong-Foy, Antek G.; Matzger, Adam J.
  • Journal of the American Chemical Society, Vol. 130, Issue 33, p. 10870-10871
  • DOI: 10.1021/ja8036096

White Phosphorus Is Air-Stable Within a Self-Assembled Tetrahedral Capsule
journal, June 2009


Systematic Design of Pore Size and Functionality in Isoreticular MOFs and Their Application in Methane Storage
journal, January 2002

  • Eddaoudi, Mohamed; Kim, Jaheon; Rosi, Nathaniel
  • Science, Vol. 295, Issue 5554, p. 469-472
  • DOI: 10.1126/science.1067208

Carbon Dioxide Capture in Metal–Organic Frameworks
journal, September 2011

  • Sumida, Kenji; Rogow, David L.; Mason, Jarad A.
  • Chemical Reviews, Vol. 112, Issue 2, p. 724-781
  • DOI: 10.1021/cr2003272

Water Adsorption in Porous Metal–Organic Frameworks and Related Materials
journal, March 2014

  • Furukawa, Hiroyasu; Gándara, Felipe; Zhang, Yue-Biao
  • Journal of the American Chemical Society, Vol. 136, Issue 11, p. 4369-4381
  • DOI: 10.1021/ja500330a

Engineering Metal Organic Frameworks for Heterogeneous Catalysis
journal, August 2010

  • Corma, A.; García, H.; Llabrés i Xamena, F. X.
  • Chemical Reviews, Vol. 110, Issue 8, p. 4606-4655
  • DOI: 10.1021/cr9003924

Functional Molecular Flasks: New Properties and Reactions within Discrete, Self-Assembled Hosts
journal, April 2009

  • Yoshizawa, Michito; Klosterman, Jeremy K.; Fujita, Makoto
  • Angewandte Chemie International Edition, Vol. 48, Issue 19, p. 3418-3438
  • DOI: 10.1002/anie.200805340

Hydrocarbon Separations in a Metal-Organic Framework with Open Iron(II) Coordination Sites
journal, March 2012


The Cambridge Structural Database
journal, April 2016

  • Groom, Colin R.; Bruno, Ian J.; Lightfoot, Matthew P.
  • Acta Crystallographica Section B Structural Science, Crystal Engineering and Materials, Vol. 72, Issue 2, p. 171-179
  • DOI: 10.1107/S2052520616003954

Enantioselective catalysis with homochiral metal–organic frameworks
journal, January 2009

  • Ma, Liqing; Abney, Carter; Lin, Wenbin
  • Chemical Society Reviews, Vol. 38, Issue 5, p. 1248-1256
  • DOI: 10.1039/b807083k

A short history of SHELX
journal, December 2007

  • Sheldrick, George M.
  • Acta Crystallographica Section A Foundations of Crystallography, Vol. 64, Issue 1, p. 112-122
  • DOI: 10.1107/S0108767307043930

Postsynthetic Methods for the Functionalization of Metal–Organic Frameworks
journal, September 2011

  • Cohen, Seth M.
  • Chemical Reviews, Vol. 112, Issue 2, p. 970-1000
  • DOI: 10.1021/cr200179u

Highly-Selective and Reversible O2 Binding in Cr3(1,3,5-benzenetricarboxylate)2
journal, June 2010

  • Murray, Leslie J.; Dinca, Mircea; Yano, Junko
  • Journal of the American Chemical Society, Vol. 132, Issue 23, p. 7856-7857
  • DOI: 10.1021/ja1027925

Hydrogen storage and carbon dioxide capture in an iron-based sodalite-type metal–organic framework (Fe-BTT) discovered via high-throughput methods
journal, January 2010

  • Sumida, Kenji; Horike, Satoshi; Kaye, Steven S.
  • Chemical Science, Vol. 1, Issue 2, p. 184-191
  • DOI: 10.1039/c0sc00179a

Storage of Methane and Freon by Interstitial van der Waals Confinement
journal, May 2002

  • Atwood, Jerry L.; Barbour, Leonard J.; Jerga, Agoston
  • Science, Vol. 296, Issue 5577, p. 2367-2369
  • DOI: 10.1126/science.1072252