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Scrutinizing negative thermal expansion in MOF-5 by scattering techniques and ab initio calculations

Lock, Nina ; Christensen, Mogens ; Wu, Yue ; Peterson, Vanessa K. ; Thomsen, Maja K. ; Piltz, Ross O. ; Ramirez-Cuesta, Anibal J. ; McIntyre, Garry J. ; Norén, Katarina LU and Kutteh, Ramzi , et al. (2013) In Dalton Transactions 42(6). p.1996-2007
Abstract
Complementary experimental techniques and ab initio calculations were used to determine the origin and nature of negative thermal expansion (NTE) in the archetype metal-organic framework MOF-5 (Zn4O(1,4-benzenedicarboxylate) (3)). The organic linker was probed by inelastic neutron scattering under vacuum and at a gas pressure of 175 bar to distinguish between the pressure and temperature responses of the framework motions, and the local structure of the metal centers was studied by X-ray absorption spectroscopy. Multi-temperature powder-and single-crystal X-ray and neutron diffraction was used to characterize the polymeric nature of the sample and to quantify NTE over the large temperature range 4-400 K. Ab initio calculations complement... (More)
Complementary experimental techniques and ab initio calculations were used to determine the origin and nature of negative thermal expansion (NTE) in the archetype metal-organic framework MOF-5 (Zn4O(1,4-benzenedicarboxylate) (3)). The organic linker was probed by inelastic neutron scattering under vacuum and at a gas pressure of 175 bar to distinguish between the pressure and temperature responses of the framework motions, and the local structure of the metal centers was studied by X-ray absorption spectroscopy. Multi-temperature powder-and single-crystal X-ray and neutron diffraction was used to characterize the polymeric nature of the sample and to quantify NTE over the large temperature range 4-400 K. Ab initio calculations complement the experimental data with detailed information on vibrational motions in the framework and their correlations. A uniform and comprehensive picture of NTE in MOF-5 has been drawn, and we provide direct evidence that the main contributor to NTE is translational transverse motion of the aromatic ring, which can be dampened by applying a gas pressure to the sample. The linker motion is highly correlated rather than local in nature. The relative energies of different framework vibrations populated in MOF-5 are suggested by analysis of neutron diffraction data. We note that the lowest-energy motion is a librational motion of the aromatic ring which does not contribute to NTE. The libration is followed by transverse motion of the linker and the carboxylate group. These motions result in unit-cell contraction with increasing temperature. (Less)
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Contribution to journal
publication status
published
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Dalton Transactions
volume
42
issue
6
pages
1996 - 2007
publisher
Royal Society of Chemistry
external identifiers
  • wos:000313617500010
  • scopus:84871818910
  • pmid:23044752
ISSN
1477-9234
DOI
10.1039/c2dt31491f
language
English
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yes
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1f5bbed5-feda-4d62-a1c0-3b26d927a444 (old id 3590801)
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2016-04-01 10:10:33
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@article{1f5bbed5-feda-4d62-a1c0-3b26d927a444,
  abstract     = {Complementary experimental techniques and ab initio calculations were used to determine the origin and nature of negative thermal expansion (NTE) in the archetype metal-organic framework MOF-5 (Zn4O(1,4-benzenedicarboxylate) (3)). The organic linker was probed by inelastic neutron scattering under vacuum and at a gas pressure of 175 bar to distinguish between the pressure and temperature responses of the framework motions, and the local structure of the metal centers was studied by X-ray absorption spectroscopy. Multi-temperature powder-and single-crystal X-ray and neutron diffraction was used to characterize the polymeric nature of the sample and to quantify NTE over the large temperature range 4-400 K. Ab initio calculations complement the experimental data with detailed information on vibrational motions in the framework and their correlations. A uniform and comprehensive picture of NTE in MOF-5 has been drawn, and we provide direct evidence that the main contributor to NTE is translational transverse motion of the aromatic ring, which can be dampened by applying a gas pressure to the sample. The linker motion is highly correlated rather than local in nature. The relative energies of different framework vibrations populated in MOF-5 are suggested by analysis of neutron diffraction data. We note that the lowest-energy motion is a librational motion of the aromatic ring which does not contribute to NTE. The libration is followed by transverse motion of the linker and the carboxylate group. These motions result in unit-cell contraction with increasing temperature.},
  author       = {Lock, Nina and Christensen, Mogens and Wu, Yue and Peterson, Vanessa K. and Thomsen, Maja K. and Piltz, Ross O. and Ramirez-Cuesta, Anibal J. and McIntyre, Garry J. and Norén, Katarina and Kutteh, Ramzi and Kepert, Cameron J. and Kearley, Gordon J. and Iversen, Bo B.},
  issn         = {1477-9234},
  language     = {eng},
  number       = {6},
  pages        = {1996--2007},
  publisher    = {Royal Society of Chemistry},
  series       = {Dalton Transactions},
  title        = {Scrutinizing negative thermal expansion in MOF-5 by scattering techniques and ab initio calculations},
  url          = {http://dx.doi.org/10.1039/c2dt31491f},
  doi          = {10.1039/c2dt31491f},
  volume       = {42},
  year         = {2013},
}