Postsynthetic Addition of Ligand Struts in Metal-Organic Frameworks: Effect of Syn/Anti Addition on Framework Structures with Distinct Topologies.

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.