The Metal-organic Frameworks Constructed From Triazole And Benzenedicarboxylate And Their Gas Adsorption And Fluorescence Properties

As a new type of porous crystal materials, the metal-organic frameworks（MOFs），namely porous metal-organic coordination polymers (PMOCPs), with diversity ofstucures, tubable pore size and modification of pore surface, have attracted muchattentions recently for their potential applictions in the areas such as gas sorption andsepararion, catalysis and detection of dangerous chemical gas.To design and synthesizethe novel metal-organic frameworks with good performance has always been theresearch target of coordination chemists and material chemists，and the rational choiceof organic ligands plays a vital role in synthesizing the metal-organic framworks withexpected structures and functionalities. In this thesis, nine porous metal-organicframeworks,{[Zn(1,4-BDC)0.5(3-NH2-trz)]·(solvent)]}n(1),{[Zn(2-NH2-1,4-BDC)0.5(trz)]·(solvent)]}n(2),{[Zn(1,4-BDC)0.5(trz)]·(solvent)]}n(3),{[Zn(1,3-BDC)0.5(3-NH2-trz)]·(solvent)]}n(4),{[Zn(2-NO2-1,4-BDC)0.5(3-NH2-trz)]·(solvent)}n(5),{[Zn(2-Br-1,4-BDC)0.5(3-NH2-trz)]·(solvent)}n(6),{[Zn(2-Br-1,4-BDC)0.5(trz)]·(solvent)}n(7),[Cd1.5(1,3-BDC)(3-NH2-trz)]n(8) and [Cd(2-NH2-1,4-BDC)]n(9), based on aromatic carboxylic acid andtriazole with functional group, have been obtained by hydrothermal reaction method,which all be characterized by single-crystal X-ray diffraction, IR spectroscopy andthermogravimetric analysis. The structures of compounds1-7are three-dimentionalnetworks with one-dimensional pore which being occupied by DMF and H2Omoleculars. We try to displace the DMF and H2O moleculars with methanol molecularsby dipping the compounds1-7into the methanol solution for several days, and only inMOFs2,3and4, the DMF and H2O solvents have been swapped out. The gas sorptionproperties of the MOFs2,3and4, in which the methanol solvents have been removedby heating under vacuum, on N2and CO2have been extensively studied. Theexperimental results show that the compound2displays no any adsorption on N2under77K, but possess certain sorption performance on CO2under273K. However, thecompounds3and4both have adsorbed a certain amouts of N2under77K, and theyalso display good sorption performance on CO2under273K. Futhermore, the influenceof the reaction conditions, such as reaction time, temperature, solvent and the molarratios of metal ion and organic ligand, on crystal growth of the compounds have also been disccused in the thesis.Three parts are divided in this paper:The first chapter has mainly reviewed the concept, the synthesis strategies andsynthesis methods, the choice of organic ligands and the applications of themetal-organic frameworks, and the research work of the thesis have also been putforward.The second chapter described the syntheses and structures of the ninemetal-organic frameworks, and the thermal and chemical stabilities of which have alsobeen elucidated by TGA. The solvents with high boiling point in the pores of some ofthe MOFs have been displaced with methanol moleculars by dipping the MOFs into themethanol solutions for several days. The sorption properties of the MOFs2,3and4, inwhich the DMF and H2O moleculars have been successfully swapped out, on N2andCO2have been extensively studied. The fluorecent properties of the MOFs5,6,7,8and9have also been tested.The last chapter is the conclusion and an outlook on this thesis.