Crystal melting and vitrification behaviors of a three-dimensional nitrile-based metal–organic framework,Faraday Discussions

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Crystal melting and vitrification behaviors of a three-dimensional nitrile-based metal–organic framework
Faraday Discussions ( IF 3.3 ) Pub Date : 2020-04-09 , DOI: 10.1039/d0fd00003e
Chinmoy Das _{1,

2,

3,

4} , Satoshi Horike _{1,

2,

3,

4,

5}

Affiliation

A three-dimensional (3D) metal–organic framework [Ag(pL2)(CF₃SO₃)]·2C₆H₆ (pL2 = 1,3,5-tris(4-cyanophenylethynyl)benzene), composed of Ag⁺ and tripodal nitrile ligands, was prepared to enable the investigation of its crystal melting and vitrification behaviors. The guest-free state showed a crystal melting at 271 °C, and the liquid state transformed into a glassy state via cooling. The vitrification of the crystalline compound into an amorphous glassy state was also obtained by mechanical hand-grinding. The structure of the glassy state retained the 3D networked structure, confirmed by FT-IR, X-ray absorption, and scattering measurements. The mechanically induced glass showed a small uptake of CO₂ and a strong affinity for benzene and H₂O vapors, confirmed by gas sorption isotherms. Powder X-ray diffraction studies have revealed that the vitrified structure returned to the original 3D crystalline structure by exposure to these vapors.

中文翻译：

三维腈基金属-有机骨架的晶体熔化和玻璃化行为

三维（3D）金属-有机骨架[Ag（p L2）（CF ₃ SO ₃）]·2C ₆ H ₆（p L2 = 1,3,5-三（4-氰基苯基乙炔基）苯）制备了Ag ⁺和三脚架腈配体，以研究其晶体熔化和玻璃化行为。无客体状态显示晶体在271°C时熔化，并且液态通过冷却。结晶化合物的玻璃化也变成无定形玻璃态，这是通过机械手工研磨获得的。FT-IR，X射线吸收和散射测量证实了玻璃态的结构保留了3D网络结构。机械诱导的玻璃显示出少量的CO ₂吸收以及对苯和H ₂ O蒸气的强亲和力，这已通过气体吸附等温线证实。粉末X射线衍射研究表明，玻璃化结构通过暴露于这些蒸气而恢复为原始3D晶体结构。

更新日期：2020-04-09

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