Synthese,Structures And Characterization Of Novel Coordination Polymers Base On N-heterocyclic Derivatives Bridge Ligands

In the past decade years, remarkable progress in the field of supermolecular chemistry and crystal engineering has been witnessed in the study of metal-organic coordination polymers（or metal-organic frameworks, MOFs）, not only due to their extensive potential applications in catalysis, separation, ion-exchange, as well as their aesthetic topology and intriguing structures. With the development of crystallography and related disciplines, through the selection of organic ligands and metal ions to synthesize the coordination polymers with special structures has attracted much attention. The aim of this thesis is to synthesize a series of novel metal-organic coordination polymers which perhaps exhibit well photoluminescence or magnetic properties, on the basis of N-heterocyclic derivatives and metal salts by hydrothermal technique, to further study the principle of synthesis as well as the relationships between the structures and properties for these novel metal-organic coordination polymers.A series of new metal-organic coordination polymers have been synthesized by hydrothermal. The structures were characterized by elemental analyses, ICP, IR spectra,single-crystal X-ray diffraction analyses and X-ray powder diffraction（XRPD）. The thermal stabilities（TG）, magnetic properties and fluorescent activity of these compounds have been studied, as well.1. Five new metal-organic coordination polymers with different types of entanglement have been hydrothermally synthesized on the bases of N-heterocyclic derivative bridge ligands, that are,[Zn₂（bdc）_1.5（dbpp）]（1）[Cd（dbpp）₂（H₂O）·（H₂O）]（2）[Co（dbpp）₂]（3）[Cu（tyty）]（4）[Cu_1.5（L1）（L2）（tyty）]（5）（dbpp = 4-{1-[4-（2,5-Dihydro-1H-tetrazol-5-yl）-benzyl]-1H-pyrazol-3-yl}-pyridine, bdc= 1,4-benzenedicarboxylate acid, HL1 = 2,3,4,5-tetrachlorobenzoic acid, HL2 =2,3,4,5,6-pentachlorobenzoic acid, Htyty = 1-（tetrazp-5-yl）-4（trizo-1-yl）benzene）.Compound 1 is a fascinating 3D self-penetrated architecture. Compound 2 exhibits a peculiar（2D → 3D） polycatenated motif and single network contains double edges.Compound 3 displays fascinating entangled frameworks which have both interdigitation and pseudo-polyrotaxane characters. Compound 4 reveals a 2D double-bilayer sheet;additionally each sheet is interdigitated by two adjacent layers in a parallel fashion to yield an unusual 2D → 3D interdigitated frameworks. Compound 5 displays a 2D layer built by tyty anions and rod-shaped SBUs, and 2D sheets further exhibit a 2D → 3D interdigitated network.2. Three new metal-organic coordination polymers have been hydrothermally synthesized on the bases of N-heterocyclic derivative carboxylic ligands, that are,[Co（ppmba）₂]（6）[Zn（ppmba）₂（H₂O）_0.5]（7）[Cd（ppmba）₂·（H₂O）_0.25]（8）（Hppmba = 4-（（3-（pyridin-4-yl）-1H-pyrazol-1-yl）methyl）benzoic acid）. Compound6 is a peculiar（2D → 3D） interdigitated architecture that is assembled from bilayer motifs. Compounds 7 and 8 exhibit fascinating（2D → 3D） entangled frameworks constructed from undulating 44-sql layers, which have both polycatenane and interdigitation characters.The main contents of this paper are as follows:In the first chapter, the formation and development, synthesis methods of the coordination polymers, and the properties, the application and the classification of coordination polymers are discussed. Introduces the background, purpose and the main results about the experiments. And introduces the chemical reagents, experimental instruments and the main testing methods required in the experimental process.In the second chapter, the nitrogen heterocyclic bridged ligands and metal ions successful synthesized five cases of new metal-organic coordination polymers. The synthesis method, crystal structure, characterization and properties of new coordination polymers.In the third chapter, the N-heterocyclic carboxylic acid ligands and metal ions successful synthesized three cases of new metal-organic coordination polymers. The synthesis method, crystal structure, characterization and properties of new coordination polymers.