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Title: Defining the Proton Topology of the Zr6 -Based Metal–Organic Framework NU-1000

Abstract

Metal–organic frameworks (MOFs) constructed from Zr6-based nodes have recently received considerable attention given their exceptional thermal, chemical, and mechanical stability. Because of this, the structural diversity of Zr6-based MOFs has expanded considerably and in turn given rise to difficulty in their precise characterization. In particular it has been difficult to assign precisely where protons (needed for charge balance) reside on some Zr6-based nodes. Elucidating the precise proton topologies in Zr6-based MOFs will have wide ranging implications in defining their chemical reactivity, acid/base characteristics, conductivity and chemical catalysis. Here we have used a combined quantum mechanical and experimental approach to elucidate the precise proton topology of the Zr6-based framework NU-1000. Lastly, our data indicate that a mixed node topology, [Zr63–O)43-OH)4(OH)4(OH2)4]8+, is preferred and simultaneously rules out five alternative node topologies.

Authors:
 [1];  [2];  [1];  [1];  [1];  [2];  [3];  [1]
  1. Univ. of Minnesota, Minneapolis, MN (United States)
  2. Northwestern Univ., Evanston, IL (United States)
  3. Northwestern Univ., Evanston, IL (United States); King Abdulaziz Univ., Jeddah (Saudi Arabia)
Publication Date:
Research Org.:
Univ. of Minnesota, Minneapolis, MN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1458981
Grant/Contract Number:  
FG02-12ER16362; SC0008688
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry Letters
Additional Journal Information:
Journal Volume: 5; Journal Issue: 21; Journal ID: ISSN 1948-7185
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; node topology; density functional theory; IR spectroscopy; tautomerism

Citation Formats

Planas, Nora, Mondloch, Joseph E., Tussupbayev, Samat, Borycz, Joshua, Gagliardi, Laura, Hupp, Joseph T., Farha, Omar K., and Cramer, Christopher J. Defining the Proton Topology of the Zr6 -Based Metal–Organic Framework NU-1000. United States: N. p., 2014. Web. doi:10.1021/jz501899j.
Planas, Nora, Mondloch, Joseph E., Tussupbayev, Samat, Borycz, Joshua, Gagliardi, Laura, Hupp, Joseph T., Farha, Omar K., & Cramer, Christopher J. Defining the Proton Topology of the Zr6 -Based Metal–Organic Framework NU-1000. United States. doi:10.1021/jz501899j.
Planas, Nora, Mondloch, Joseph E., Tussupbayev, Samat, Borycz, Joshua, Gagliardi, Laura, Hupp, Joseph T., Farha, Omar K., and Cramer, Christopher J. Fri . "Defining the Proton Topology of the Zr6 -Based Metal–Organic Framework NU-1000". United States. doi:10.1021/jz501899j. https://www.osti.gov/servlets/purl/1458981.
@article{osti_1458981,
title = {Defining the Proton Topology of the Zr6 -Based Metal–Organic Framework NU-1000},
author = {Planas, Nora and Mondloch, Joseph E. and Tussupbayev, Samat and Borycz, Joshua and Gagliardi, Laura and Hupp, Joseph T. and Farha, Omar K. and Cramer, Christopher J.},
abstractNote = {Metal–organic frameworks (MOFs) constructed from Zr6-based nodes have recently received considerable attention given their exceptional thermal, chemical, and mechanical stability. Because of this, the structural diversity of Zr6-based MOFs has expanded considerably and in turn given rise to difficulty in their precise characterization. In particular it has been difficult to assign precisely where protons (needed for charge balance) reside on some Zr6-based nodes. Elucidating the precise proton topologies in Zr6-based MOFs will have wide ranging implications in defining their chemical reactivity, acid/base characteristics, conductivity and chemical catalysis. Here we have used a combined quantum mechanical and experimental approach to elucidate the precise proton topology of the Zr6-based framework NU-1000. Lastly, our data indicate that a mixed node topology, [Zr6(μ3–O)4(μ3-OH)4(OH)4(OH2)4]8+, is preferred and simultaneously rules out five alternative node topologies.},
doi = {10.1021/jz501899j},
journal = {Journal of Physical Chemistry Letters},
number = 21,
volume = 5,
place = {United States},
year = {2014},
month = {10}
}

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Works referencing / citing this record:

Cooperative Cluster Metalation and Ligand Migration in Zirconium Metal-Organic Frameworks
journal, October 2015

  • Yuan, Shuai; Chen, Ying-Pin; Qin, Junsheng
  • Angewandte Chemie International Edition, Vol. 54, Issue 49
  • DOI: 10.1002/anie.201505625

Non-3d Metal Modulation of a Cobalt Imidazolate Framework for Excellent Electrocatalytic Oxygen Evolution in Neutral Media
journal, December 2018

  • Xu, Yan-Tong; Ye, Zi-Ming; Ye, Jia-Wen
  • Angewandte Chemie International Edition, Vol. 58, Issue 1
  • DOI: 10.1002/anie.201809144

Modulator-Controlled Synthesis of Microporous STA-26, an Interpenetrated 8,3-Connected Zirconium MOF with the the-i Topology, and its Reversible Lattice Shift
journal, March 2018

  • Bumstead, Alice M.; Cordes, David B.; Dawson, Daniel M.
  • Chemistry - A European Journal, Vol. 24, Issue 23
  • DOI: 10.1002/chem.201705136

Assembly of dicobalt and cobalt–aluminum oxide clusters on metal–organic framework and nanocast silica supports
journal, January 2017

  • Desai, Sai Puneet; Malonzo, Camille D.; Webber, Thomas
  • Faraday Discussions, Vol. 201
  • DOI: 10.1039/c7fd00055c

Synthesis and proton conductivity of two novel molybdate polymers
journal, January 2018

  • Xu, Li; Wang, Zhifang; Lu, Ying
  • New Journal of Chemistry, Vol. 42, Issue 20
  • DOI: 10.1039/c8nj03781g

Instantaneous Hydrolysis of Nerve-Agent Simulants with a Six-Connected Zirconium-Based Metal-Organic Framework
journal, May 2015

  • Moon, Su-Young; Liu, Yangyang; Hupp, Joseph T.
  • Angewandte Chemie International Edition, Vol. 54, Issue 23
  • DOI: 10.1002/anie.201502155

Destruction of chemical warfare agents using metal–organic frameworks
journal, March 2015

  • Mondloch, Joseph E.; Katz, Michael J.; Isley III, William C.
  • Nature Materials, Vol. 14, Issue 5
  • DOI: 10.1038/nmat4238

Instantaneous Hydrolysis of Nerve-Agent Simulants with a Six-Connected Zirconium-Based Metal-Organic Framework
journal, May 2015

  • Moon, Su-Young; Liu, Yangyang; Hupp, Joseph T.
  • Angewandte Chemie International Edition, Vol. 54, Issue 23
  • DOI: 10.1002/anie.201502155

Cooperative Cluster Metalation and Ligand Migration in Zirconium Metal-Organic Frameworks
journal, October 2015

  • Yuan, Shuai; Chen, Ying-Pin; Qin, Junsheng
  • Angewandte Chemie International Edition, Vol. 54, Issue 49
  • DOI: 10.1002/anie.201505625

Non-3d Metal Modulation of a Cobalt Imidazolate Framework for Excellent Electrocatalytic Oxygen Evolution in Neutral Media
journal, December 2018

  • Xu, Yan-Tong; Ye, Zi-Ming; Ye, Jia-Wen
  • Angewandte Chemie International Edition, Vol. 58, Issue 1
  • DOI: 10.1002/anie.201809144

Modulator-Controlled Synthesis of Microporous STA-26, an Interpenetrated 8,3-Connected Zirconium MOF with the the-i Topology, and its Reversible Lattice Shift
journal, March 2018

  • Bumstead, Alice M.; Cordes, David B.; Dawson, Daniel M.
  • Chemistry - A European Journal, Vol. 24, Issue 23
  • DOI: 10.1002/chem.201705136

Destruction of chemical warfare agents using metal–organic frameworks
journal, March 2015

  • Mondloch, Joseph E.; Katz, Michael J.; Isley III, William C.
  • Nature Materials, Vol. 14, Issue 5
  • DOI: 10.1038/nmat4238

Assembly of dicobalt and cobalt–aluminum oxide clusters on metal–organic framework and nanocast silica supports
journal, January 2017

  • Desai, Sai Puneet; Malonzo, Camille D.; Webber, Thomas
  • Faraday Discussions, Vol. 201
  • DOI: 10.1039/c7fd00055c

Synthesis and proton conductivity of two novel molybdate polymers
journal, January 2018

  • Xu, Li; Wang, Zhifang; Lu, Ying
  • New Journal of Chemistry, Vol. 42, Issue 20
  • DOI: 10.1039/c8nj03781g