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

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Thomsen, Maja K. Ramirez-cuesta, Anibal J. Norén, Katarina Lock, Nina Peterson, Vanessa K. Kearley, Gordon J. Piltz, Ross O. Wu, Yue Kepert, Cameron J. Mcintyre, Garry J. Kutteh, Ramzi Christensen, Mogens Iversen, Bo B.
Description	Author Affiliation: Lock N ( Center for Materials Crystallography, Dept. of Chemistry and iNANO, Aarhus University, 8000 Aarhus C, Denmark.)
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 $(Zn_{4}O(1,4-benzenedicarboxylate)_{3}).$ 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.
ISSN	14779226
Issue Number	6
Journal	Dalton Trans.
Volume Number	42
e-ISSN	13645447
Language	English
Publisher	Royal Society of Chemistry
Publisher Date	2013-02-14
Publisher Place	Great Britain (UK)
Access Restriction	Subscribed
Subject Keyword	Chemistry
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

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