Synthesis,Luminescence Sensing Properties And Iodine Capture Of Zirconocene-based Molecular Capsules

The design and synthesis of polyhedrons by the self-assembly of coordination between molecular and metal has always been an important topic for chemists.Metal-organic molecular capsules(MCs)are discrete molecular entities with specific cavities that are self-assembled by organic ligands and metal-based sub-building units(SBUs).In recent years,metal-organic molecular capsules have been developing rapidly,playing an important role in catalysis,gas adsorption,biomedicine,molecular sensing and other fields.Zirconium-based building units have flexible coordination sites and strong oxyphilicity.The design and synthesis of new metal-organic materials with zirconium clusters as building units and small molecular carboxylic acids as connectors is a hot topic in materials chemistry research.In this paper,we choose the trinuclear zirconium cluster{Cp₃Zr₃(?₃-O)(?₂-OH)₃}as building unit,using different configurations of dicodontocarboxylic acid as the connector,which enable us to successfully prepare six kinds of crystalline compounds under solvothermal conditions:{[Cp₃Zr₃(?₃-O)(?₂-OH)₃]₂(BDC)₃}·Cl₂(DMA)(H₂O)(1){[Cp₃Zr₃(?₃-O)(?₂-OH)₃]₂(SDC)₃}·Cl₂(DMF)_2.5(2){[Cp₃Zr₃(?₃-O)(?₂-OH)₃]₂(ADA)₃}·Cl₂(DMF)₂(3){[Cp₃Zr₃(?₃-O)(?₂-OH)₃]₂(L¹)₃}·Cl₂(DMF)₂(4){[Cp₃Zr₃(?₃-O)(?₂-OH)₃]₄(BDC)₆}·Cl₄(DMA)₄(5){[Cp₃Zr₃(?₃-O)(?₂-OH)₃]₂(L²)₂}(DMA)₂(6)L¹=2,2-Bipyridine-4,4-dicarboxylic acid L²=5-SulfoisophthalicacidThese compounds were characterized by elemental analysis,XRD,PXRD,TGA,IR and UV-Vis.Compounds 1-4 are all capsule cationic compounds.Compound 5 and Compound 6 were novel window-type compounds.Compounds 2 exhibits a luminescence quenching effect towards Fe³⁺ions,suggesting that it possesses a potential ability in the applications of fluorescence probes and biological detection of Fe³⁺.Moreover,the sorption and release performance of Compounds 1,3 and 5 for iodine were investigated.