真空诱导客体，'-二乙酰胺在亚稳态 Cd 基金属有机骨架中的结合。

Vacuum-Induced Guest ,'-Diethylformamide Binding in a Metastable Cd-Based Metal-Organic Framework.

机构信息

College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, China.

College of Engineering, Information Technology and Environment, Charles Darwin University, Darwin, Northern Territory 0909, Australia.

出版信息

Inorg Chem. 2022 Dec 19;61(50):20227-20231. doi: 10.1021/acs.inorgchem.2c03549. Epub 2022 Dec 2.

DOI:10.1021/acs.inorgchem.2c03549

PMID:36458998

Abstract

A three-dimensional (3D) metal-organic framework (MOF) of [EtNH][Cd(BTB)(DEF)]·4.75DEF (; HBTB = benzene-1,3,5-tribenzoic acid and DEF = ,'-diethylformamide) sustained by symmetrical Z-shaped Cd secondary building units (SBUs) with an intrinsically metastable host framework has been prepared and characterized. Upon gentle vacuum (800 Pa) at 50 °C, some encapsulated DEF solvates are released, leading to pore-shape changes and Cd coordination geometry distortion. This is followed by DEF solvate migration to only one end of the SBU with concomitant symmetry breaking. Additional time under vacuum promoted further structural distortion and topology changes as authenticated by single-crystal X-ray diffraction studies. This work was initially inspired by unusual gas adsorption isotherms and points to the potentially complicated, nonspectator role of coordinative solvents such as DEF during MOF activation.

摘要

一种由 [EtNH][Cd(BTB)(DEF)]·4.75DEF（; HBTB = 苯-1,3,5-三苯甲酸，DEF =,'-二乙基甲酰胺）组成的三维（3D）金属有机骨架（MOF），由对称 Z 形 Cd 次级建筑单元（SBUs）支撑，具有内在不稳定的主框架已被制备和表征。在温和的真空（800 Pa）和 50°C 下，一些包裹的 DEF 溶剂化物被释放，导致孔形状的变化和 Cd 配位几何形状的扭曲。随后，DEF 溶剂化物迁移到 SBU 的一端，同时伴随对称性的破坏。在真空下进一步延长时间会促进进一步的结构变形和拓扑结构变化，这一点已通过单晶 X 射线衍射研究得到证实。这项工作最初是受到不寻常的气体吸附等温线的启发，并指出在 MOF 活化过程中，配位溶剂如 DEF 可能具有复杂的、非旁观者的作用。