Uncovering Structural Opportunities for Zirconium Metal–Organic Frameworks via Linker Desymmetrization

Abstract The discovery of metal–organic frameworks (MOFs) mimicking inorganic minerals with intricate topologies requires elaborate linker design guidelines. Herein, the concept of linker desymmetrization into the design of tetratopic linker based Zr‐MOFs is applied. A series of bent tetratopic linkers with various substituents are utilized to construct Zr‐MOFs with distinct cluster connectivities and topologies. For example, the assembly between a bent linker L‐SO2 with C2v symmetry and an 8‐connected Zr6 cluster leads to the formation of an scu topology, while another flu topology can be obtained by the combination of a novel 8‐connected Zr6 cluster and a bent linker L‐O with C1 symmetry. Further utilization of restricted bent linker [(L‐(CH3)6)] gives rise to a fascinating (4, 6)‐c cor net, originated from the corundum lattice, with an unprecedented 6‐c Zr6 cluster. In addition, the removal of toxic selenite ions in aqueous solution is performed by PCN‐903‐(CH3)6 which exhibits rapid and efficient detoxification. This work uncovers new structural opportunities for Zr‐MOFs via linker desymmetrization and provides novel design strategies for the discovery of sophisticated topologies for practical applications.

Abstract licence: CC BY

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