【作者】 房超；

【导师】 董育斌；

【作者基本信息】 山东师范大学 ， 有机化学， 2011， 硕士

【摘要】 近年来,配位作用驱动的超分子体系的设计、合成和性质研究引起了化学家们浓厚的兴趣与广泛的关注。化学家们利用自组装方法合成了众多配位作用驱动的超分子体系,得到了许多分子组装的新的构建模型,并发现了一批具有新奇物理和化学性质的新材料。本文合成了一系列结构新颖的开链冠醚桥连的有机配体以及双Schiff-base配体,并研究它们在水热及溶剂条件下与金属离子的自组装化学。共合成了20个新型的配位化合物,通过红外、元素分析、X-射线单晶衍射及粉末衍射等方法表征了它们的结构,并对部分化合物的阴离子交换与荧光性质进行了研究。一、合成了两例对称双Schiff-base有机配体,并研究了它们与过渡金属Cd（II）、Ag（I）的配位化学,得到了5个结构新颖的配位聚合物:{Cd（L₁）（SCN）₂}n （1）、{Cd（L1）₂（OTf）₂·3THF}n （2）、{Ag——2（L₂）₂（PF₆）₂·2CH₃OH}n （3）、{Ag₂（L₂）₂（SbF₆）₂·CH-3OH·H₂O}n （4）、{Ag（L₂）（ClO₄）·0.5CH3OH·0.25THF}n （5）,并表征和讨论了它们的晶体结构。其中3、4、5是同构的具有一维管状隧道的超分子组装体,在隧道中填充有不同的平衡阴离子,这为我们进行阴离子交换提供了条件。二、利用双Schiff-base配体与Ag（I）自组装所合成的超分子化合物3、4、5,进行了阴离子交换和荧光性质研究。讨论了阴离子与主体框架之间的弱相互作用,实现了不同阴离子对主体荧光发射的调控。三、合成了一系列开链冠醚桥连的有机配体,研究了它们在水热及溶剂条件下与过渡金属M（II）（M = Cu、Hg、Cd、Ni和Zn）和Ag（I）的配位化学,合成了10个结构新颖的配位化合物:{Cu（L₃）₂（NO₃）₂} （6）、{Ni_0.5（L₃）Cl·CH₃CN} （7）、{Cu（L₃）₂（ClO₄）₂} （8）、{Cu（L₃）₂（ClO₄）₂} （9）、{Hg（L₃）_0.5I₂} （10）、{Cd_0.5（L₄）（SCN）·CH₃CN}_n （11）、{Cu₂（L5）₂（SCN）₂（ClO₄）₂·0.5CH₃OH·0.5H₂O} （12）、{Cd₂（L₅）₃ （ClO₄）₄·2.5CH₃OH·CH₂Cl₂} （13）、{Ag₂（L6）₂（SbF₆）₂} （14）、{Cu（L₇）Cl₂}n （15）,并表征和讨论了它们的晶体结构。四、将芳香羧酸共配体引入到超分子体系中,介绍了开链冠醚配体L3及芳香羧酸与金属的混配自组装化学,合成了5个结构新颖的配位聚合物:{Cu₂（L₃）₂（C₈H₄O₄）₂·3H₂O}n （16）、{Cd（L₃）（C₈H₄O₄）·2H₂O}n （17）、{Cu（L₃） （C₉H₄O₆）·H₂O}n （18）、{Cu（L₃）（C₉H₄O6）·H₂O}n （19）、{Cd（L₃）（4, 4’-bpy）₂（ClO₄）₂·4H₂O}_n （20）。讨论了共配体对配位化合物结构的影响,并研究了它们的固态荧光性质。我们设计合成了一系列结构新颖的开链冠醚桥连的有机配体及对称双Schiff-base配体,并研究了它们与过渡金属的自组装化学。研究结果证明这些配体是构建结构新颖的超分子组装体的良好前体。此外,我们还对部分化合物的阴离子交换性质与荧光性质进行了初步研究,为设计合成可调谐发光材料及功能材料奠定了实验基础。更多还原

【Abstract】 The design and construction of coordination-driven supramolecular complexes are recently attracting significant interest and extensive attention. Currently, chemists have synthesized numerous supramolecular complexes through the approach of self-assembly and thus constructed novel materials with remarkable physical and chemical properties. In this thesis, a series of novel open-chain polyether-bridged ligands and double Schiff-base ligand were synthesized. The self-assembly chemistry based on these new ligands and metal ions under hydrothermal and solvent conditions was investigated. Totally 20 new coordination compounds were prepared and fully characterized by IR, elemental analysis, X-ray single-crystal diffraction and powdered X-ray diffraction. The anion-exchange and luminescent properties based on some compounds were investigated.1. Two symmetrical Schiff-base ligands were synthesized, and we have investigated their coordination chemistry with Cd（II）, Ag（I） salts. Five new coordination polymers were synthesized based on them: {Cd（L₁）（SCN）₂}n （1）, {Cd（L₁）₂（OTf）₂·3THF}_n （2）, {Ag₂（L₂）2（PF₆）2·2CH₃OH}n （3）, {Ag₂（L₂）₂（SbF₆）₂·CH₃OH·H₂O}n （4）, {Ag（L₂）（ClO₄）·0.5CH₃OH·0.25THF}n （5）, and their cystal structure were discussed as well. Besides, compounds 3, 4, 5 are the isomorphic nano-tubes with one-dimension channel, and in the channel there are different anions. This provides possibility for the study of anion-exchange.2. We have investigated anion-exchange and luminescent properties based on compounds 3, 4, 5. The weak interactions between anions and host frameworks were demonstrated. The tunable fluorescence emission based on these supramolecular systems were successfully realized.3. A series of open-chain polyether-bridged ligands were synthesized. The coordination chemistry based on open-chain polyether-bridged ligands and inorganic Cu（II）, Hg（II）, Cd（II）, Ni（II）, Zn（II） and Ag（I） salts has been investigated. Ten new supramolecular compounds were synthesized based on them: {Cu（L₃）₂（NO₃）₂} （6）, {Ni_0.5（L₃）Cl·CH₃CN} （7）, {Cu（L₃）₂（ClO₄）₂} （8）, {Cu（L₃）₂（ClO₄）₂} （9）, {Hg（L₃）_0.5 I2} （10）, {Cd0.5（L4_）（SCN）·CH₃CN}n （11）, {Cu₂（L₅）2（SCN）₂（ClO₄）₂·0.5CH₃OH·0.5H₂O} （12）, {Cd₂（L5）₃（ClO₄）₄·2.5CH₃OH·CH₂Cl₂} （13）, {Ag₂（L₆）₂（SbF₆）₂} （14）, {Cu（L7） Cl₂}n （15）, and their cystal structures were characterized.4. The aromatic acid was introduced into the supramolecular complexes. The self-assembly chemistry based on ligand L3, aromatic acid and metal ions under hydrothermal condition was investigated, five new supramolecular compounds were synthesized based on them: {Cu₂（L₃）₂（C₈H₄O₄）₂·3H₂O}_n （16）, {Cd（L3）（C₈H₄O₄）·2H₂O}n （17）, {Cu（L₃）（C₉H₄O₆）·H₂O}_n （18）, {Cu（L₃）（C₉H₄O₆）·H₂O}_n （19）, {Cd（L₃） （4, 4’-bpy）₂（ClO₄）2·4H₂O}_n （20）. The results demonstrated that aromatic acid has the impact on the structure of coordination compounds, and their luminescent properties were investigated in the solid state.In this thesis, a series of novel open-chain polyether-bridged ligands and double Schiff-base ligand were synthesized. The self-assembly chemistry based on these new ligands and metal ions was investigated. The results indicate that these new ligands are the favorable precursors of constructing novel supramolecular complexes. Futhermore, anion-exchange and luminescent properties based on some compounds have been investigated. This sets experiment foundation for designing and synthesing tunable luminescent materials and functional materials.更多还原