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 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 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 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.
Keywords: linker design; linker desymmetrization; metal–organic frameworks; topology; zirconium.
© 2019 The Authors. Published by WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim.