Coordination Polymers Based On Flexible Aromatic Carboxylic Acid And Nitrogen-Containing Ligands: Syntheses, Structures And Properties

Nowadays, design and synthesize of novel functional coordination polymers have been one of the hottest research topic in coordination chemistry, materials chemistry, biochemistry, supramolecular chemistry and crystal engineering. It not only due to their novel topological structures, but also for their huge potential applications in the optoelectronic materials, magnetic materials, molecular switches, gas storage, selective catalytic, bio-medical, molecular recognition and self-assembly fields. The aim of the research is to construct coordination polymers with excellent fluorescence through hydrothermal synthesis of rare earth ion (TbⅢ), transition metal ions (FeⅢ,CdⅡ,ZnⅡ) and main group metal ions (PbⅡ,BaⅡ) with two kinds of flexible aromatic carboxylic acids and three kinds of nitrogen-containing ligands, respectively. Finally, we have successfully synthesized three series, eight coordination polymers which are all roundly characterized by the method of X-ray single crystal diffraction, elemental analyses, IR spectra, thermal gravimetric analyses, and luminescence analyses. This dissertation includes four chapters as follows:(1) Chapter 1:Preface. Briefly introduced the basic concepts, leading methods of synthesize, application fields and research priorities. Then reviewed the research development of coordination polymers constructed by the muti-pyridine ligands and flexible aromatic carboxylic acids. The basis and significance of topic selection and research production with this dissertation were also briefly recommended at length.(2) Chapter 2:Two novel TbⅢ和FeⅢcoordination compounds based on 3,3',4,4'-oxydiphthalic acid (H4odpa) and ramification of 1,10-phenanthroline have been successfully synthesized. Complex 1 shows a 2D network, while 2 assumes a mononuclear structure which can be developed by the coaction of H-bond andπ-πstacking. The influence of the center metal ions effect on the structure of compounds is also systematically studied.(3) Chapter 3:Coordination polymers 3-6 are constructed by d10 transition metals, 3,3',4,4'-diphenylsulfonetetracarboxylic acid (H4dpst) and nitrogen-containing ligands. The compounds 3-5 are all 2D planar network structures, while compound 6 presented a different 3D stratiform structure. The different structures between 3-6 provide some useful information on studying the influence by metal ions and organic ligands. The result of luminescent and thermal gravimetric analyses indicates that they all take on high thermal stability. Further more, they all have potential application value as green and blue fluorescence materials.(4) Chapter 4:Based on d10 transition metal, main group metals, 3,3',4,4'-diphenylsulfonetetracarboxylic acid (H4dpst) and 1,10-phenanthroline, we have synthesized two novel heterobimetallic coordination polymers 7-8 for the first time. Compound 7 shapes a 2D planar network by function ofμ3-OH- bridging andπ-πstacking between parallel 1,10-phenanthroline ligands. While compound 8 is a 2D network containing 1D Ba-O chains. Two compounds both have excellent luminescent and high thermal stability.Summing up the conditions of hydrothermal synthesis, such as metal ions, organic ligands, solvent, rate of materials, and so on, which are the important effects on the structure of products. The impacts of the coordination polymer structure on luminous performance are also discussed.