Cargando…

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

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 devel...

Descripción completa

Detalles Bibliográficos
Autores principales: Gonzalez, Miguel I., Mason, Jarad A., Bloch, Eric D., Teat, Simon J., Gagnon, Kevin J., Morrison, Gregory Y., Queen, Wendy L., Long, Jeffrey R.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Royal Society of Chemistry 2017
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5580307/
https://www.ncbi.nlm.nih.gov/pubmed/28966783
http://dx.doi.org/10.1039/c7sc00449d
_version_ 1783260883526352896
author Gonzalez, Miguel I.
Mason, Jarad A.
Bloch, Eric D.
Teat, Simon J.
Gagnon, Kevin J.
Morrison, Gregory Y.
Queen, Wendy L.
Long, Jeffrey R.
author_facet Gonzalez, Miguel I.
Mason, Jarad A.
Bloch, Eric D.
Teat, Simon J.
Gagnon, Kevin J.
Morrison, Gregory Y.
Queen, Wendy L.
Long, Jeffrey R.
author_sort Gonzalez, Miguel I.
collection PubMed
description 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 Co(2)(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 Co(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.
format Online
Article
Text
id pubmed-5580307
institution National Center for Biotechnology Information
language English
publishDate 2017
publisher Royal Society of Chemistry
record_format MEDLINE/PubMed
spelling pubmed-55803072017-09-29 Structural characterization of framework–gas interactions in the metal–organic framework Co(2)(dobdc) by in situ single-crystal X-ray diffraction Gonzalez, Miguel I. Mason, Jarad A. Bloch, Eric D. Teat, Simon J. Gagnon, Kevin J. Morrison, Gregory Y. Queen, Wendy L. Long, Jeffrey R. Chem Sci Chemistry 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 Co(2)(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 Co(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. Royal Society of Chemistry 2017-06-01 2017-04-19 /pmc/articles/PMC5580307/ /pubmed/28966783 http://dx.doi.org/10.1039/c7sc00449d Text en This journal is © The Royal Society of Chemistry 2017 http://creativecommons.org/licenses/by-nc/3.0/ This is an Open Access article distributed under the terms of the Creative Commons Attribution-NonCommercial 3.0 Unported License (http://creativecommons.org/licenses/by-nc/3.0/) which permits unrestricted non-commercial use, distribution, and reproduction in any medium, provided the original work is properly cited.
spellingShingle Chemistry
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 Co(2)(dobdc) by in situ single-crystal X-ray diffraction
title Structural characterization of framework–gas interactions in the metal–organic framework Co(2)(dobdc) by in situ single-crystal X-ray diffraction
title_full Structural characterization of framework–gas interactions in the metal–organic framework Co(2)(dobdc) by in situ single-crystal X-ray diffraction
title_fullStr Structural characterization of framework–gas interactions in the metal–organic framework Co(2)(dobdc) by in situ single-crystal X-ray diffraction
title_full_unstemmed Structural characterization of framework–gas interactions in the metal–organic framework Co(2)(dobdc) by in situ single-crystal X-ray diffraction
title_short Structural characterization of framework–gas interactions in the metal–organic framework Co(2)(dobdc) by in situ single-crystal X-ray diffraction
title_sort structural characterization of framework–gas interactions in the metal–organic framework co(2)(dobdc) by in situ single-crystal x-ray diffraction
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5580307/
https://www.ncbi.nlm.nih.gov/pubmed/28966783
http://dx.doi.org/10.1039/c7sc00449d
work_keys_str_mv AT gonzalezmigueli structuralcharacterizationofframeworkgasinteractionsinthemetalorganicframeworkco2dobdcbyinsitusinglecrystalxraydiffraction
AT masonjarada structuralcharacterizationofframeworkgasinteractionsinthemetalorganicframeworkco2dobdcbyinsitusinglecrystalxraydiffraction
AT blochericd structuralcharacterizationofframeworkgasinteractionsinthemetalorganicframeworkco2dobdcbyinsitusinglecrystalxraydiffraction
AT teatsimonj structuralcharacterizationofframeworkgasinteractionsinthemetalorganicframeworkco2dobdcbyinsitusinglecrystalxraydiffraction
AT gagnonkevinj structuralcharacterizationofframeworkgasinteractionsinthemetalorganicframeworkco2dobdcbyinsitusinglecrystalxraydiffraction
AT morrisongregoryy structuralcharacterizationofframeworkgasinteractionsinthemetalorganicframeworkco2dobdcbyinsitusinglecrystalxraydiffraction
AT queenwendyl structuralcharacterizationofframeworkgasinteractionsinthemetalorganicframeworkco2dobdcbyinsitusinglecrystalxraydiffraction
AT longjeffreyr structuralcharacterizationofframeworkgasinteractionsinthemetalorganicframeworkco2dobdcbyinsitusinglecrystalxraydiffraction