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Title: Defining the Proton Topology of the Zr 6 -Based Metal–Organic Framework NU-1000

Metal–organic frameworks (MOFs) constructed from Zr 6-based nodes have recently received considerable attention given their exceptional thermal, chemical, and mechanical stability. Because of this, the structural diversity of Zr 6-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 Zr 6-based nodes. Elucidating the precise proton topologies in Zr 6-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 Zr 6-based framework NU-1000. Lastly, our data indicate that a mixed node topology, [Zr 63–O) 43-OH) 4(OH) 4(OH 2) 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:
Grant/Contract Number:
FG02-12ER16362; SC0008688
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
Research Org:
Univ. of Minnesota, Minneapolis, MN (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; node topology; density functional theory; IR spectroscopy; tautomerism
OSTI Identifier:
1458981

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., 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.. 2014. "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}
}