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A Computational and Experimental Approach Linking Disorder, High-Pressure Behavior, and Mechanical Properties in UiO Frameworks

DOI: 10.1002/anie.201509352 DOI Help
PMID: 26797762 PMID Help

Authors: Claire Hobday (University of Edinburgh) , Ross James Marshall (University of Glasgow) , Colin F. Murphie (University of Glasgow) , Jorge Sotelo (EaStCHEM School of Chemistry, Joseph Black Building, West Mains Road, Edinburgh) , Tom Richards (University of Cambridge) , Dave Allan (Diamond Light Source) , Tina Düren (University of Bath) , François-xavier Coudert (CNRS) , Ross Forgan (University of Glasgow) , Carole A. Morrison (University of Edinburgh) , Stephen Moggach (The University of Edinburgh) , Thomas Bennett (Department of Materials Science and Metallurgy, University of Cambridge)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Angewandte Chemie International Edition

State: Published (Approved)
Published: January 2016

Abstract: 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.

Journal Keywords: gas separation; high-pressure chemistry; metal–organic frameworks; structure elucidation; X-ray crystallography

Subject Areas: Materials, Chemistry


Instruments: I19-Small Molecule Single Crystal Diffraction