Synthesis, Structure And Properties Of The Coordination Polymers：with Carboxylate Ligands And Auxiliary Ligands

In the past two decades, metal-organic coordination polymers have attracted great attention from chemists, due to their intriguing variety of architectures and topological features as well as their potential applications as functional materials gas adsorption and separation, asymmetric catalysis, nonlinear optics and magnetic materials. In principle, the choice of building units (metal ions and organic ligands) and the synthetic pathways play an important role on the assembly of metal-organic coordination polymers. So far, a lot of organic ligands with different functional groups have been designed for assemblies of various coordination polymers with differerent dimensionality. In this paper, coordinated polymers with carboxylate ligands and auxiliary ligands have been synthesized through hydro(solvo)thermal techniques. The coordination polymers were characterized by elemental analysis, infrared spectra, XRD, thermogravimetric analysis, X-ray single-crystal diffraction, etc. And some coordination polymers fluorescence properties are also discussed. This paper includes the following five chapters:In the first chapter, we systematically introduce the basic conception and development of the coordination polymers and the research progress of coordination polymers with carboxylate ligands and auxiliary ligands as well as the significance and the progress made in this topic.In the second chapter, we introduce four novel coordination polymers coordination polymers [Cd(tbta)(bbi)]n (1),[Zn(tbta)(bbi)]n (2),[Ni(tbta)(bpp)]·(H2O)2(3) and [Mn(tbta)(bpp)2]·(H2O)2(4) have been successfully synthesized by using auxiliary ligands and2,3,5,6-tetrabromoterephthalic acid. Both compounds1and2are2D layera (4,4) layer structures. Compound3is a3D framework. The structure of Compound4is a1D linear chain which chould construct a3D three-dimensional supramolecular assembly with H-bonds in4.In the third chapter, two novel coordination polymers [Cd2(sdba)2(bbi)]n (5) and [Zn(sdba)(bbi)]·2H2O (6) have been generated by using auxiliary ligands, 4,4’-sulfonyldibenzoic acid ligands and metal ions under the solvothermal conditions through select different solvents. The structure of5contains four nuclear cadmium clusters [Cd4(COO)8(bbi)4]. It is a three-dimensional (3D) coordination polymer, which can be simplified as a46.64network structure. The structure of6contains two nuclear zinc clusters [Zn2(COO)4N2], which is a2D infinite network.In the fourth chapter, one new2D coordination polymers [Ni(fipbb)(bpe)]n (7) has been successfully synthesized.7was prepared solvothermal starting from NiCl2,2,2-bis(4-carboxyphenyl)-hexafluoropropanc and1,2-di(4-pyridinyl)ethene in110℃. The structure of7is a2D layer which could construct a three-dimensional supramolecular assembly with H-bonds.In the conclusion, the structure and function of seven coordination polymers and the influence of solvent and template agent on the coordination polymer structure have been summarized. The research provided a new route for design and synthesis of new functional polymers with carboxylate ligands and auxiliary ligands.