1. Halogenated Metal-Organic Framework Glasses and Liquids
- Author
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Dean S. Keeble, Alice M. Bumstead, Aoife McCaul, Thomas D. Bennett, Bun Chan, Gregor Mali, Philip A. Chater, Dominique R. T. Appadoo, Vicki Chen, Jingwei Hou, Zeyu Deng, David A. Keen, Rijia Lin, Adam F. Sapnik, María Laura Ríos Gómez, Shichun Li, and Andraž Krajnc
- Subjects
Steric effects ,Terahertz radiation ,General Chemistry ,010402 general chemistry ,01 natural sciences ,Biochemistry ,Catalysis ,0104 chemical sciences ,Crystal ,chemistry.chemical_compound ,Colloid and Surface Chemistry ,chemistry ,Imidazolate ,Physical chemistry ,Metal-organic framework ,Deformation (engineering) ,Zeolitic imidazolate framework - 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 metal-organic framework (MOF) glasses improves their gas-uptake properties.
- Published
- 2020