A computational and experimental approach linking disorder, high-pressure behavior, and mechanical properties in UiO frameworks

Hobday, C. L. et al. (2016) A computational and experimental approach linking disorder, high-pressure behavior, and mechanical properties in UiO frameworks. Angewandte Chemie (International Edition), 55(7), pp. 2401-2405. (doi: 10.1002/anie.201509352) (PMID:26797762)

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Whilst many metal–organic frameworks possess the chemical stability needed to be used as functional materials, they often lack the physical strength required for industrial applications. Herein, we have investigated the mechanical properties of two UiO-topology Zr-MOFs, the planar UiO-67 ([Zr6O4(OH)4(bpdc)6], bpdc: 4,4′-biphenyl dicarboxylate) and UiO-abdc ([Zr6O4(OH)4(abdc)6], abdc: 4,4′-azobenzene dicarboxylate) by single-crystal nanoindentation, high-pressure X-ray diffraction, density functional theory calculations, and first-principles molecular dynamics. On increasing pressure, both UiO-67 and UiO-abdc were found to be incompressible when filled with methanol molecules within a diamond anvil cell. Stabilization in both cases is attributed to dynamical linker disorder. The diazo-linker of UiO-abdc possesses local site disorder, which, in conjunction with its longer nature, also decreases the capacity of the framework to compress and stabilizes it against direct compression, compared to UiO-67, characterized by a large elastic modulus. The use of non-linear linkers in the synthesis of UiO-MOFs therefore creates MOFs that have more rigid mechanical properties over a larger pressure range.

Item Type:Articles
Glasgow Author(s) Enlighten ID:Forgan, Professor Ross and Marshall, Mr Ross James
Authors: Hobday, C. L., Marshall, R. J., Murphie, C. F., Sotelo, J., Richards, T., Allan, D. R., Duren, T., Coudert, F.-X., Forgan, R. S., Morrison, C. A., Moggach, S. A., and Bennett, T. D.
College/School:College of Science and Engineering > School of Chemistry
Journal Name:Angewandte Chemie (International Edition)
Publisher:Wiley - V C H Verlag GmbH & Co. KGaA
ISSN (Online):1521-3773
Published Online:21 January 2016
Copyright Holders:Copyright © 2016 The Authors
First Published:First published in Angewandte Chemie (International Edition) 55(7): 2401-2405
Publisher Policy:Reproduced under a Creative Commons License

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Project CodeAward NoProject NamePrincipal InvestigatorFunder's NameFunder RefLead Dept
619471Biomimetic guest selective metal-organic frameworks: catalysis and self-assemblyRoss ForganEngineering & Physical Sciences Research Council (EPSRC)EP/L004461/1CHEM - CHEMISTRY