Synthesis And Application Of Coordination Polymer Based On Rigid Polydentate Ligand

Coordination polymers is a material formed by self-assembly of metal ions or clusters with ligands through coordination,compared with traditional materials,it's novel structure,high porosity,high specific surface area and adjustable channel structure broad application prospects in gas adsorption and separation,fluorescence identification,catalysis,drug delivery,nonlinear optics and other fields.However,it is still a great challenge to realize the controllable synthesis and directional application of coordination polymers by external stimulation.Focusing on the controllable synthesis and directional application of coordination polymers,this paper not only realized the controllable self-assembly of chiral coordination polymers,but also prepared porous coordination polymers that can accurately identify the isomers of nitroaniline and selectively capture carbon dioxide molecules.This paper includes the following five parts:In chapter 1,the development of coordination polymers is reviewed,the classification and synthesis of coordination polymers are introduced,and the applications of coordination polymers in different fields are discussed.In chapter 2,using chiral Zn2Cd cluster and(1,3,5-Tri-(4-carboxypHenyl)benzene(H3BTB)ligand directly self-assembly synthesis of chiral compounds 1([Zn2Cd(BTB)2(H2O)2]·0.5DEF·4H2O),and add the suitable amount of pyridine in the system can get chiral compound 2([Zn2Cd(BTB)2(H2O)2](Py)6(DEF)2(H20)7(EtOH)).Further studies showed that the chiral self-assembly process of pyridine plays the role of coordination template,and the chiral induction process can be further regulated by adjusting the temperature.By further controlling this chiral process,we also obtained the key intermediate compound 3 involved in the pyridine template and explained the chiral origin induced by pyridine through this key intermediate.Through the directional modification of pyridine template,the chiral orientation control of a large amount of compound 2 samples was also realized.This work is a chiral inducing pHenomenon which is different from the traditional symmetry breaking crystallization,and will provide a new idea for the chiral origin in nature and the design and synthesis of chiral coordination polymers.In chapter 3,a novel three-dimensional coordination polymer 4([Zn(DTBDA)](DMA)(MeOH)2(H2O)3.5)with hexagonal macropore structure was constructed by using ligand 3'-5' di(1 h-1,2,4-triazol-1-yl)-[1,1'-bipHenyl]-3(5-dicarboxylic acid)and zinc.Compound 4 can not only accurately identify three nitroaniline isomers,but also quantitatively detect benzaldehyde from benzyl alcohol.Further study found that the discriminant detection was derived from the exact matching of the emission peak of compound 4 and the absorption peak of different nitroaniline isomers.This work will provide a new idea for the development of fluorescent sensors that can accurately decode isomers.In chapter 4,ligand 3'-5' di(1h-1,2,4-triazol-1-yl)-[1,1'-bipHenyl]-3,5-dicarboxylic acid(H2DTBDA)and zinc and cobalt were self-assembled to synthesize 3 example coordination polymers with ultrapore structure 5([Zn(DTBDA)](DMA)(H2O)3.5),6([Zn(DTBDA)](CH4O)(DEF)0.33(H2O)1.67).7([Zn(DTBDA)](DMA)0.66(CH4O)0.66(H2O)3).Compounds 6 and 7 are converted to compounds 8(Zn(DTBDA))and 9(Co(DTBDA))during activation.Compounds 5,8,and 9 have a good separation efficiency of carbon dioxide/nitrogen and carbon dioxide/methane at room temperature and pressure.The breakthrough experiments further confirmed the usefulness of compounds 5 and 8.The theoretical calculation indicates that the good carbon dioxide selectivity of compound 5 comes from the synergistic action of the microporous confined cavity and the active site.This work will provide potential ideas for the development of practical carbon dioxide capture agents.In chapter 5,we summarizes the work of this paper and the future prospects.