Halogenated Metal-Organic Framework Glasses and Liquids
Halogenated Metal-Organic Framework Glasses and Liquids
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DOI：
10.1021/jacs.9b11639
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发表时间：
2020-02-26
影响因子：
15
通讯作者：
Bennett, Thomas D.
中科院分区：
文献类型：
--
作者：
Hou, Jingwei;Rios Gomez, Maria Laura;Bennett, Thomas D.
据报道，使用混合配体方法合成了四种新型结晶沸石咪唑酯骨架（ZIF）结构。咪唑酯和卤代苯并咪唑酯衍生的连接体的包含导致所有四种结构的玻璃形成行为。据观察，熔化温度取决于电子效应和空间效应。固态核磁共振和太赫兹 (THz)/远红外证明氟化 ZIF 玻璃中存在 Zn-F 键。原位太赫兹/远红外光谱技术揭示了卤化 ZIF 的晶体、玻璃和液相的动态结构特性，将 ZIF 的熔化行为与 ZnN4 四面体发生热致变形的倾向联系起来。金属有机骨架（MOF）玻璃中包含卤化配体可改善其气体吸收性能。
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.