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Halogenated metal-organic framework glasses and liquids

DOI: 10.1021/jacs.9b11639 DOI Help

Authors: Jingwei Hou (University of Cambridge; University of Queensland) , María Laura Ríos Gómez (University of Cambridge; Ciudad Universitaria) , Andraž Krajnc (National Institute of Chemistry) , Aoife Mccaul (University of Cambridge) , Shichun Li (University of Cambridge; Institute of Chemical Materials, China Academy of Engineering Physics) , Alice M. Bumstead (University of Cambridge) , Adam F. Sapnik (University of Cambridge) , Zeyu Deng (University of Cambridge) , Rijia Lin (University of Queensland) , Philip A. Chater (Diamond Light Source) , Dean S. Keeble (Diamond Light Source) , David A. Keen (ISIS Facility) , Dominique Appadoo (Australian Synchrotron) , Bun Chan (Nagasaki University) , Vicki Chen (University of Queensland) , Gregor Mali (National Institute of Chemistry, Slovenia) , Thomas D. Bennett (University of Cambridge)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Journal Of The American Chemical Society

State: Published (Approved)
Published: January 2020
Diamond Proposal Number(s): 20038

Abstract: The synthesis of four novel crystalline zeolitic imidazolate framework (ZIF) structures using a mixed-ligand approach is reported. The inclusion of both imidazolate and halogenated benzimidazolate-derived linkers leads to glass-forming behavior by all four structures. Melting temperatures are observed to depend on both electronic and steric effects. Solid-state NMR and terahertz (THz)/Far-IR demonstrate the presence of a Zn-F bond for fluorinated ZIF glasses. In situ THz/Far-IR spectroscopic techniques reveal the dynamic structural properties of crystal, glass and liquid phases of the halogenated ZIFs, linking the melting behavior of ZIFs to the propensity of the ZnN4 tetrahedra to undergo thermally-induced deformation. The inclusion of halogenated ligands within MOF-glasses improves their gas uptake properties.

Journal Keywords: Metal-organic framework; Glass; Liquid; Melting; Solid-state NMR; THz/Far-IR; Dynamic Properties

Subject Areas: Materials, Chemistry


Instruments: I15-1-X-ray Pair Distribution Function (XPDF)

Other Facilities: Australian Synchrotron