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

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 C-2v symmetry and an 8-connected Zr-6 cluster leads to the formation of an scu topology, while another flu topology can be obtained by the combination of a novel 8-connected Zr-6 cluster and a bent linker L-O with C-1 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 Zr-6 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.