Coordination Polymers Based on Nitrogen-Containing Carboxylic Acid and Biphenyl Carboxylic Acid Ligands:Synthesis and Adsorption/Separation Properties

Author:Bai Zuo Zuo

Supervisor:wang yao yu


Degree Year:2019





Coordination polymers(CPs)possess the characteristics of both organic ligands and inorganic metal ions,and have unique properties due to their structure’s designability and clippability.As a new type of material,its research spans coordination chemistry,physical chemistry,organic chemistry,material chemistry,crystal engineering,supramolecular chemistry and topography,etc.Metal-Organic Frameworks(MOFs)as a kind of porous coordination polymers,take inorganic metal and organic ligand as nodes and linkers,respectively,forming 1D chain,2D layer and 3D framework structures through the coordination bonds and other weak interactions(hydrogen bond,π-πinteraction and van der Waals force),displaying wide application prospect.While because of various synthetic reactants,such as the choice of metal ions and organic linkers(from small organic molecules to macrocyclic ligands,from multiple carboxylic acid ligands to nitrogen heterocyclic ligands),the designable synthesis of CPs with specific functions still has challenging difficulty.In recent years,the study of CPs has made remarkable achievements,not only because of its charming structure,but also because of the constantly updated development of science and technology,test method and synthetic method,it shows huge potential application value in optics,catalysis,molecular magnetism,adsorption/separation,etc.In this thesis,we mainly discussed the construction and function of CPs in magnetic,gas adsorption/separation and separation of liquid xylene isomers.In chapter Ⅰ,we introduced the development history of coordination chemistry and the concepts of CPs and MOFs;secondly,we briefly introduced the synthesis strategy of this kind of material;finally,we mainly introduced the application of this material in magnetic,gas adsorption/separation,and also introduced the application of MOFs in the separation of liquid mixtures.In chapter Ⅱ,five multifarious dimensional complexes{[Zn(dtp)]·H2O}(1),{[Zn(dtp)]·2CH3OH·NMP}(2),{[Mn(dtp)2(H2O)4]·7(H2O)}(3),{[Mn(Hdtp)(Cl)]}(4)and{[Mn(dtp)(H2O)]·1.5H2O}(5)werepreparedviasolvothemalreactionof4’-(3,5-dicarboxyphenyl)-2,2’:6’,2’’-terpyridine(H2dtp)with Zn(Ⅱ)/Mn(Ⅱ)ions.We analyzed the structural characteristics of the five CPs.The magnetic property of 3,4 and 5,the photoluminescence property of 1 and 2,as well as the adsorption property of 2 which shows an unusual stepwise adsorption,have also been investigated.In chapter Ⅲ,five multifarious dimensional CPs{[Co3(L)2(H2O)2]·4H2O}(6),{[Cd3(L)2(NMP)2]}(7),{[Cu(HL)]·NMP}(8),{[Cd(HL)(2,2’-bipy)]}(9)and{[Co(HL)(4,4’-bipy)(H2O)2]}(10)were prepared via solvothemal reaction of5-(3,4-dicarboxylphenoxy)nicotic acid ligand and auxiliary 2,2’-bipy or 4,4’-bipy co-ligands with Co(Ⅱ)/Cu(Ⅱ)/Cd(Ⅱ)ions.6 demonstrates the effective storage capacity for CO2 as well as high selectivity for CO2 over CH4.Complexes 6,8 and 10 exhibit antiferromagnetic behaviours.Also,the alternating-current susceptibility of 10 displays slow magnetic relaxation,showing interesting magnetic behaviour of a single-chain magnet with an effective energy barrier of 8.98 K.In chapter Ⅳ,we report the discrimination of xylene isomers via refining pore size in a series of porous MOFs,MFM-300(Al,Fe,V,In,Cr)and NOTT-101(Cu)at a sub-angstrom precision,leading to the optimal chromatographic separation of all three xylene isomers in these materials at room temperature.The exceptional performance of MFM-300(Fe,V,In)for xylene separation has been reinforced by dynamic ternary breakthrough experiments.In-depth structural and vibrational investigations using synchrotron X-ray diffraction have been futher studyed.