Topology-Guided Stepwise Insertion of Three Secondary Linkers in Zirconium Metal–Organic Frameworks

We report a topology-guided, precise insertion of three distinct secondary linkers into a zirconium-based metal–organic framework, NPF-300. Constructed from a tetratopic linker L and Zr6 cluster, NPP-300 exhibits a unique scu topology and certain flexibility along the crystallographic a axis, and in conjunction with the conformation change of the primary ligand, is able to accommodate the stepwise insertion of three different secondary linkers along the a and c axes. Size-matching and mechanic strain of the resulting framework are two important factors that determine the chemical stability of the inserted linkers. Secondary linker insertion in NPF-300 significantly enables not only its porosity but also potentials to install up to three different functional groups for the construction of multivariate MOFs with homogeneity.

Xin ZhangBrandon L. FreyYu-Sheng Chen, and Jian Zhang* 

 Department of Chemistry, University of Nebraska—Lincoln, Lincoln, Nebraska 68588, United States

 ChemMatCARS, Center for Advanced Radiation Sources, The University of Chicago, 9700 South Cass Avenue, Argonne, Illinois 60439, United States

Adapted with permission from J. Am. Chem. Soc., 2018, 140(24), pp 7710-7715. Copyright 2018 American Chemical Society.