【作者】 肖娟；

【导师】 黄晓春；

【作者基本信息】 汕头大学 ， 无机化学， 2011， 硕士

【摘要】 具有丰富的配位模式,并能结合含氮、羧酸基团配体优点的含氮杂环羧酸类配体,已被广泛的用来构筑了大量新颖的结构。这些配位聚合物在气体存储和选择性分离、催化、药物储存与释放、手性以及光、电、磁等方面表现出来的潜在应用价值。本论文的主要工作是基于5-羧基苯并三氮唑（H2btca）配体在溶剂热条件下制备结构新颖的多功能配合物。本文主要分为五章。第一章对配位聚合物的最新研究动态进行了简要介绍;基于一些特殊结构与功能性配合物等进行了归纳总结;简要的介绍了苯并三氮唑类配体的研究现状,并阐述本论文的研究目的和意义。第二章系统地研究了通过对溶剂的调控,成功地合成出3个Cu（II）配合物。它们分别为[Cu（btca）（H₂O）₂] （1） , [Cu（btca）（H₂O）3.5]·H₂O （2） ,[Cu_2.5（btca）(H_0.5btca)（μ2-Cl）_0.5（μ3-OH）（H₂O）]·H₂O （3）。由于水分子对结构的影响,得到了两个假性超分子异构体,配合物1是二维平面结构,配合物2是首例平面金属大环氢键纳米管状结构;而配合物3在改变溶剂的条件下,引入了氯离子,形成了具有蜂窝状孔洞的三维结构。详细的磁性测试表明配合物1²为反铁磁体;配合物3在低温下呈现出弱的铁磁性行为。第三章主要探讨了在溶剂热的反应条件下合成的3个Zn（II）配合物,[Zn（btca）（H₂O）] （4）,[Zn（btca）（H₂O）]·_2.5H₂O （5）,[Zn₃（btca）₂（μ3-OH）₂]·DMF·4H₂O （6）。其中配合物4和5属于假性的同分异构体,而配合物6是具有sra拓扑网络的柔性多孔结构,可受热导致结构发生变化,存在特殊的温度、溶剂敏感现象。同时具备孔性和荧光性质的柔性配合物是十分罕见的。第四章合成了三个Cd（II）配合物,[Cd（Hbtca）₂] （7）,[Cd（btca）（H₂O）₂] （8）,[Cd（btca）] （9）。配体在配合物中由于反应条件的影响使其以不同价态的阴离子形式存在。其中,配合物7是具有钻石拓扑网络的三重穿插结构;配合物8是一维链状结构;而配合物9是一个十分致密的三维结构。该系列的镉金属配合物能发射较强的荧光。最后对论文进行概括总结,并展望了下一阶段的工作安排。更多还原

【Abstract】 Ditopic ligands containing carboxylic and nitrogen donor groups have been widely used to architect novel coordination polymers. These complexes possess potential applications in gas storage, adsorption based gas/vapor separation, shape/size-selective catalysis, drug storage and delivery, optical, electrical and magnetism properties. We mainly introduce the construction of the novel and multifunctional complexes based on benzotriazole-5-carboxylate acid （H2btca） under hydro-（solvo-） thermal reaction. This thesis is divided into five chapters.In chapter 1, the research background is concisely introduced with emphasis on the current survey in the area of coordination polymers. Some special structures and multifunctional coordination polymers are mainly summarized. The history and actuality of some notable compounds based on ligands contained different characteristics of the groups are briefly reviewed. In addition, the intention and significance of coordination polymers based on benzotriazole-5-carboxylate acid are also elucidated.In chapter 2, we report the syntheses of three novel coordination complexes by reactions of transition metal ions with H2btca under hydro（solvo）thermal reaction conditions, [Cu（btca）(H₂O₂] （1）, [Cu（btca）（H₂O）3.5]·H₂O （2）, [Cu_2.5（btca）(H_0.5btca)（μ2-Cl）_0.5（μ3-OH）（H₂O）]·H₂O （3）. Compound 1 is two dimensional （2D） network. And compound 2 represents the first example of a neutral flattened metallomacrocycle-based hydrogen-bonded nanotubular structure. Nevertheless, compound 3 is a 3D metal-organic framework encompassing a considerable solvent-accessible volume with 1D honeycomb channels. Detailed magnetic measurement exhibits anti-ferromagnetic behavior of 1² and weak ferromagnetic behavior at low temperature of 3 .In chapter 3, [Zn（btca）（H₂O）] （4）, [Zn（btca）（H₂O）]·_2.5H₂O （5）, [Zn3(btca₂(μ3-OH₂]·DMF·4H₂O （6） have been self-assembled with transition metal ions Zn（II） and H2btca ligand. It is noteworthy that 4 and 5 are pseudo-supramolecular isomers, which are produced from the influence of water. Besides, Compound 6 exhibits great flexibility （the so-called“breathing”） which has obvious variation in unit cell volume by heating. All of the materials exhibit intense fluorescent emission wherein 6 presents interesting guest-dependent photoluminescent property. What’s more, this multifunctional material combined with flexible porosity and intense photoluminescence is very rare.Chapter 4 focuses on reactions of H2btca ligand and cadmium ions Cd（II）, which indicates that metal ions and solvents take essential role on these structures of the three complexes as followed: [Cd（Hbtca）₂] （7）, [Cd（btca）（H₂O）₂] （8）, [Cd（btca）] （9）. The results indicate that the ligand is deprotonated to form different anionic derivatives in the obtained complexes. Compound 7 features three-fold interpenetrated net with diamond-like topology. 8 and 9 exhibit diverse superstructures, one dimensional （1D） chain, 3D close-grained network, respectively. In addition, these complexes exhibit fluorescence emissions.Finally, the main achievements and conclusions in this thesis are summarized. The further research plan in this project has also been proposed.更多还原