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.