【作者】 宋哲；

【导师】 冯守华；

【作者基本信息】 吉林大学 ， 无机化学， 2008， 博士

【摘要】 本论文主要研究在水热反应体系下,含氮、含氧配体过渡金属化合物的合成和表征。旨在合成具有新颖结构的化合物,并在合成研究的基础上,探讨特殊结构化合物的合成条件、成因以及有机组分对无机结构的影响作用。研究体系主要包括五元含氮杂环1,2,4-三氮唑配体构筑的配位聚合物,四环方酸配体构筑的配位聚合物及直链丁炔二酸配体构筑的配位聚合物。利用单晶X-射线衍射等多种表征手段对系列合成产物的结构与相关性能进行表征及测试。论文具体内容包括由1,2,4-三氮唑与过渡金属锌/镉合成的配位聚合物(第二章),由方酸和丁炔二酸配体与不同过渡金属合成的配位聚合物(第三章)。论文还阐述了上述化合物的合成条件与方法,有机配体对结构的影响,热稳定性以及特殊结构形成的原因,为含氮、含氧配体过渡金属配位聚合物的进一步研究奠定了基础。更多还原

【Abstract】 The research of metal-organic coordination polymer remains an extremely active field of materials chemistry in recent years. According to the principle of the crystal engineering, it is possible to control the structure of the coordination polymer at a certain extent. At the same time, coordination polymer can be endowed with some properties, such as catalysts, adsorption, nonlinear optical activity, electrics and magnetism. As the properties of the coordination polymers is determined by their chemical constituents and framework topologies, seeking the coordination polymers with the novel topology has been considered as the exploiting the functional properties of the coordination polymers. Latest years, many research groups at home and abroad get a lot of great fruits in design, synthesis and functional development according to the principle of the crystal engineering. However, the synthesis mechanism is still not known due to the terrible complexity of the synthesis-chemistry in coordination polymer. So it is need to deeply research and accumulates abundant experimental facts, finally to achieve the aims of molecular design and directional synthesis. A useful way of producing supramolecular structures is based on complementarity and selectivity of the ligands, which are crucial for coordination polymers using noncovalent interactions such as hydrogen bonding,π···π, C–A···π, cation···π, anion···π, etc. The small molecules reveal noncovalent interactions as major forces that stabilize supramolecular structures. So far, the bridging ligands containing O- or N- donors through either covalent bonds or weaker intermolecular interactions are used to bind metal centers, generating a number of one- two- and threedimensional infinite frameworks.We synthesized some coordination polymers after rationally designing the bridging ligands and metals according to the principle of the crystal engineering. In the mean time, we studied the mainly factors on the synthesis of coordination polymers via changing the metal ions to adjust the inorganic components or ligands to adjust the framework components. On the base of large tests, we synthesized some coordination polymers with novel structures using different ligands, and summarized the rules of synthesis. Influences of other experimental factors, such as reaction temperatures, reaction times, pH values and molar ratios of the starting materials etc on the composition, the structures, purity and crystallinity of the final products were studied.In chapter two, a series of coordination polymers with novel structure using the 1, 2, 4-triazole ligands, [Zn₂（C₂H₂N₃）₃Cl] （1）, [Cd₃（C₂H₂N₃）4Cl₂]·0.25H₂O （2）, [Zn₂（C₂H₂N₃）2（C₂O₄）] （3）, [Zn（C₂H₂N₃）（CH₃COO）] （4）, [Zn₃（C₂H₂N₃）₂（C₇H₅O₂）₄] （5）, [Zn（C₂H₂N₃）（C₈O₄H₅）] （6）, [Zn₄（C₂H₂N₃）₄（C₇H₄O₂F）₄]·0.5H₂O （7） and [Zn₄（C₂H₂N₃）₄（C7H₄O₂Cl）₄] （8） have been synthesized under mild conditions. Compound 1 consists of [ZnN₃Cl] tetrahedron and [ZnN₆] octahedron, which are connected by 1, 2, 4-triazole to form a 3D framework. Compound 2 consists of [CdN₄Cl] trigonal bipyramid and [CdN₄Cl₂] octahedron, which are connected by 1, 2, 4-triazole and Cl atoms to form a 3D framework. Compound 3 consists of [ZnN₃O] tetrahedron and [ZnN₂O₄] octahedron, which are connected by 1, 2, 4-triazole and oxalic acid ligands to form a 3D framework. Compound 4 consists of [ZnN₂O₂] tetrahedron and [ZnN₂O₄] octahedron, which are connected by 1, 2, 4-triazole and acetic acid ligands to form a 3D framework with nonlinear optical properties. Compound 5 consists of [ZnN₂O₂] tetrahedron and [ZnN₂O₄] octahedron, which are connected by 1, 2, 4-triazole and benzoic acid ligands to form a 3D framework with helical units. Compounds 6-8 have the same 2D layer constructed by zinc （II） with trz and carboxylate. The main difference in the structure of the three compounds is crossbedded arrangement between the layers. In order to understand the causes of this phenomenon, we studied the noncovalent intermolecular interactions in the compounds. Compound 6 shows unusual intermolecular hydrogen bonding and C–O···πinteractions, compound 7 exhibits intermolecular hydrogen bonding and C–F···πinteractions, while compound 8 only shows intermolecular C–Cl···πinteractions. It is found that the noncovalent intermolecular interactions have an influence on crystal packing. We performed the binding energy calculations at the MP2 level of theory with the 6-31++G** basis set, for the interaction of 1, 2, 4-triazole with the oxygen, fluorin and chlorin atoms. It is easy to draw the conclusion that the intermolecular interactions are induced by C–（O, F or Cl）···πinteractions.In chapter three, a series of coordination polymers using the squaric acid ligand, [Fe（C₄O₄）（H₂O）2] （9）, [Ni（C₄O₄）（H₂O）₂] （10）, [Co₃（C₄O₄）₃（H₂O）₆] （11） and [Zn（C₄O₄）（1,10-phen）（H₂O）2] （12） have been synthesized under mild conditions. Compounds 9-11 exhibit similar sodalite structure with the 4-membered square of the squarate acids acts as the basic building unit, and there are strong hydrogen bonds interactions in structures; Compound 12 is a [Zn（C₄O₄）（1,10-phen）（H₂O）₂]_∞1-D chains through squaric acid anions bridging the [Zn（1,10-phen）（H₂O）₂] units, and there are strong hydrogen bonds andπ···πinteractions. Furthermore, a series of coordination polymers using the acetylenedicarboxylic acid ligand, [Zn（C₄O₄）（2,2’-bipy）]·（H₂O）₂ （13）, [Cd（C₄O₄）（2,2’-bipy）（H₂O）]·（H₂O） （14） and [Mn（4,4’-bipy）（H₂O）₄]·（C₄O₄）·4H₂O （15） have been synthesized under mild conditions. Compound 13 exhibits one dimensional chain structure which is repeated by the -[Zn（2,2’-bipy）（H₂O）₂]-C₄O₄- unit, and is extended to two dimensional layer structure by interaction of hydrogen bonds between chains; Compound 14 exhibits two dimensional layer structure which is linked by [Cd（2,2’-bipy）（H₂O）]²⁺ and [C₄O₄]^2- units; Compound 15 is a 3-D supramolecular structure with acetylenedicarboxylic acid anions bridging the [Mn（4,4’-bipy）（H₂O）₄]²⁺∞anions through hydrogen bonds interactions.更多还原