【作者】 李娜；

【导师】 胡怀明；

【作者基本信息】 西北大学 ， 物理化学， 2010， 硕士

【摘要】 设计和合成新型功能配位聚合物已经成为配位化学、材料化学、生物化学、超分子化学、晶体工程学等领域的研究热点,这是因为新型功能配位聚合物不仅具有新颖的拓扑结构,而且在光电材料、磁性材料、分子开关、气体贮存、选择性催化、生物医药、分子识别与自组装等领域表现出巨大的应用潜力。本论文以构筑具有荧光性能的配位聚合物为研究目标,选用稀土离子(TbⅢ)、过渡金属离子(FeⅢ、CdⅡ、ZnⅡ)和主族金属离子(PbⅡ、BaⅡ)分别与两种柔性芳香多羧酸、三种含氮配体在水热条件下反应,成功合成出三个系列共八个不同维度的配合物,运用X-射线单晶衍射解析了晶体结构,并通过元素分析、红外光谱、热重分析、荧光等实验手段进行了表征。全文共分为四章,各章内容如下：第一章前言。简单介绍了配位聚合物的基本概念、主要合成方法、应用领域及研究热点。其次介绍了多吡啶类和柔性芳香多羧酸类配位聚合物的研究进展。最后介绍了本论文的选题依据及意义和研究成果。第二章利用3,3′,4,4′-氧化二苯四羧酸(H2odpa)和邻菲咯啉衍生物构筑了两个结构新颖的TbⅢ、FeⅢ配合物1-2。配位聚合物1为二维网络结构。配合物2为单核结构,但它可由氢键和π-π堆积的共同作用拓展为三维网络。系统研究了中心金属离子的改变对配合物结构的影响。第三章利用3,3′,4,4′-砜基二苯四羧酸(H4dpst)和两种含氮配体合成了四个d10过渡金属配位聚合物3-6。配合物3-5为二维平面结构,而配合物6为三维层状结构,这为探索金属离子和有机配体对配合物结构的影响提供了有益的信息。对配合物3-6的荧光和热重分析实验表明它们具有很高的热稳定性,而且可作为蓝色和绿色荧光材料而具有潜在的应用价值。第四章首次利用3,3′,4,4′-砜基二苯四羧酸(H4dpst)、1,10-邻菲咯啉、d10过渡金属和主族金属构筑了两个结构新颖的异金属配位聚合物7-8。配合物7借助μ3-OH-的桥联作用和平行的1,10-邻菲咯啉之间强烈的π-π堆积拓展为二维平面结构。而配合物8是一个含有一维Ba-O链的二维网络结构。两个配合物都具有优异的荧光性能和较高的热稳定性。论文最后总结了八个配合物的合成条件,如金属离子、有机配体、溶剂、投料比等因素对水热合成产物结构的影响。探讨配位聚合物结构对发光性质的影响。更多还原

【Abstract】 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.更多还原