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J Am Chem Soc. 2018 Jun 20;140(24):7710-7715. doi: 10.1021/jacs.8b04277. Epub 2018 Jun 12.

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

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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.


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.


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