| Accompanying the upgrade of technology,materials science has developed a series of very fascinating organic-metal materials(MOMs),such as discrete metal-organic polyhedra(MOPs)and metal-organic frameworks(MOFs).These materials are made from metal ions or clusters(Secondary Building Units,SBUs)and organic ligands.Such materials have attractive topological structure,functional adjustability and appropriate pore size,which shows a great application potential in sensing,gas storage and separation,catalysis,magnetism,and biomedicine and many other fields.However,in the light of the reversibility of the coordination bond,several MOFs and MOPs have poor stability,which limits their practical applications in most research fields.With the relatively stable Zr-O bond(Zr-O bond energy:776 k J mol-1),this challenge has been successfully overcome by using zirconium oxygen clusters as SBUs.In recent years,the research on metal-organic polyhedrons based on trinuclear zirconium clusters has become increasingly extensive,while there are few studies on heterogeneous metal-organic frameworks based on trinuclear zirconium clusters.This paper is mainly divided into the following two parts:1.A new zirconium-based metal-organic polyhedron(Compound 1)was successfully synthesized from Bis(cyclopentadienyl)zirconium dichloride and 2,5-pyridinedicarboxylic acid under solvothermal condition.It was characterized by single-crystal X-ray diffraction,powder X-ray diffraction,thermogravimetric analysis and infrared spectroscopy.Four trinuclear zirconocene building blocks as well as six linear carboxylate ligands constitute its tetrahedral configuration.Interestingly,Compound 1 possesses considerable reversible iodine sorption performance in the organic phase,and its optimal adsorption capacity is 283 mg g-1.The related kinetics absorption and desorption process were fully investigated by multiple complementary experiments and the adsorbed iodine species(I-and I3-)in Compound 1 were further identified through crystallographic analyses.This work provides new possibilities for developing new and functional zirconium-based molecular cages materials.{[Cp3Zr3?3-O(?2-OH)3]4(PYDC)6}·Cl4·14DMA·10H2O(1)2.Under solvothermal conditions,two new types of heterogeneous metal-organic frameworks(Compound 2 and 4)were successfully synthesized from zirconocene dichloride,isonicotinic acid and cuprous chloride/nickel chloride by the one-pot method.Compound 3was prepared from p-aminobenzoic acid and zirconium dichlorobenzene under solvothermal conditions.Compound 2 was characterized by single-crystal X-ray diffraction,powder X-ray diffraction,thermogravimetric analysis and infrared spectroscopy.The iodine adsorption and release of Compound 2 were also studied.This work provides new possibilities for the development of novel functional heterogeneous metal-organic framework materials.{[Cp3Zr3?3-O(?2-OH)3]2(INA)6(Cu Cl2O)3}(H2O)·Cl2(2)[Cp3Zr3?3-O(?2-OH)3](NH2C6H4COO)3·Cl4(3){[Cp3Zr3?3-O(?2-OH)3]4(INA)12(Ni Cl2)3}·Cl16(4)... |
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