期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 142, 期 8, 页码 3880-3890出版社
AMER CHEMICAL SOC
DOI: 10.1021/jacs.9b11639
关键词
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资金
- Royal Society [UF150021, RSG\R1\ 180395, RGF \EA \180092]
- EPSRC [EP/R015481/1, EP/P022596/1]
- Australian Research Council [DE190100803]
- EPSRC
- Johnson Matthey PLC [JM11106]
- Cambridge Trust [304253100]
- Slovenian Research Agency [P1-0021, Z1-9171]
- RIKEN Information Systems Division [Q19266]
- [DP180103874]
- EPSRC [EP/R015481/1, EP/P022596/1] Funding Source: UKRI
- Australian Research Council [DE190100803] Funding Source: Australian Research Council
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.
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