金属有机框架中配体支柱的合成后添加：顺式/反式添加对具有不同拓扑结构的框架结构的影响。
Postsynthetic Addition of Ligand Struts in Metal-Organic Frameworks: Effect of Syn/Anti Addition on Framework Structures with Distinct Topologies.
作者信息
Xu Xiaoyan, Yang Fei, Han Hongliang, Xu Yanqing, Wei Wei
机构信息
Department of Chemistry , Capital Normal University , Beijing 100048 , P. R. China.
Key Laboratory of Cluster Science of Ministry of Education, Beijing Key Laboratory of Photoelectronic/Electrophotonic Conversion Materials, School of Chemistry and Chemical Engineering , Beijing Institute of Technology , Beijing 100081 , P. R. China.
出版信息
Inorg Chem. 2018 Mar 5;57(5):2369-2372. doi: 10.1021/acs.inorgchem.7b02899. Epub 2018 Feb 21.
For the parent metal-organic framework (MOF) of UiO-type 1, postsynthetic bromination (anti addition) was readily carried out on the stilbene-ligand struts by directly adding excess bromine, whereas successful hydrogenation (syn addition) can only be achieved by slowing the reaction rate; otherwise, the crystalline structure of 1 will be irreversibly damaged. Meanwhile, Kagomé-like MOF 2 can be smoothly modified by both postsynthetic bromination and hydrogenation. This study of the structural conversion not only represents the first example that adopts postsynthetic hydrogenation for modifying MOFs but also reveals various factors such as the reaction manner of syn/anti, framework topology, and reaction rate that can influence postsynthetic modification on the ligand struts of MOFs.
对于UiO-1型母体金属有机框架（MOF），通过直接添加过量溴，很容易在芪配体支柱上进行后合成溴化反应（反式加成），而成功的氢化反应（顺式加成）只能通过减缓反应速率来实现；否则，1的晶体结构将被不可逆地破坏。同时，类Kagomé MOF 2可以通过后合成溴化和氢化反应顺利进行修饰。这种结构转化的研究不仅代表了采用后合成氢化修饰MOF的首个实例，还揭示了诸如顺式/反式反应方式、框架拓扑结构以及反应速率等多种能够影响MOF配体支柱后合成修饰的因素。
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