A Breathing Zirconium Metal-Organic Framework with Reversible Loss of Crystallinity by Correlated Nanodomain Formation

Bart Bueken; Frederik Vermoortele; Matthew J Cliffe; Michael T Wharmby; Damien Foucher; Jelle Wieme; Louis Vanduyfhuys; Charlotte Martineau; Norbert Stock; Francis Taulelle; Veronique Van Speybroeck; Andrew L Goodwin; Dirk De Vos

doi:10.1002/chem.201600330

A Breathing Zirconium Metal-Organic Framework with Reversible Loss of Crystallinity by Correlated Nanodomain Formation

Chemistry. 2016 Mar 1;22(10):3264-3267. doi: 10.1002/chem.201600330. Epub 2016 Feb 11.

Authors

Affiliations

¹ Centre for Surface Chemistry and Catalysis, KU Leuven, Celestijnenlaan 200F, p. o. box 2461, 3001, Leuven, Belgium.
² Inorganic Chemistry Laboratory, University of Oxford, South Parks Road, Oxford, OX1 3QR, UK.
³ Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge, CB2 1EW, UK.
⁴ Institut für Anorganische Chemie, CAU Kiel, Max-Eyth-Strasse 2, 24118, Kiel, Germany.
⁵ Diamond Light Source, Harwell Science & Innovation Campus, Didcot, OX11 0DE, UK.
⁶ Institut Lavoisier, UMR CNRS 8180, Université de Versailles St-Quentin-en-Yvelines, Avenue des Etats-Unis 45, 78035, Versailles, France.
⁷ Center for Molecular Modeling, Ghent University, Technologiepark 903, 9052, Zwijnaarde, Belgium.
⁸ Centre for Surface Chemistry and Catalysis, KU Leuven, Celestijnenlaan 200F, p. o. box 2461, 3001, Leuven, Belgium. dirk.devos@biw.kuleuven.be.

PMID: 26865194
DOI: 10.1002/chem.201600330

Abstract

The isoreticular analogue of the metal-organic framework UiO-66(Zr), synthesized with the flexible trans-1,4-cyclohexanedicarboxylic acid as linker, shows a peculiar breathing behavior by reversibly losing long-range crystalline order upon evacuation. The underlying flexibility is attributed to a concerted conformational contraction of up to two thirds of the linkers, which breaks the local lattice symmetry. X-ray scattering data are described well by a nanodomain model in which differently oriented tetragonal-type distortions propagate over about 7-10 unit cells.

Keywords: dynamic porosity; metal-organic frameworks; phase transitions; structure elucidation; zirconium.