模块化自组装笼状超分子金属配合物的合成表征和性质研究
文献类型：学位论文
| 作者 | 姜飞 |
| 学位类别 | 博士 |
| 答辩日期 | 2012-12 |
| 授予单位 | 中国科学院研究生院 |
| 授予地点 | 北京 |
| 导师 | 阳仁强 |
| 关键词 | 自组装 笼状超分子 电化学 分子识别 |
| 学位专业 | 化学工程 |
| 中文摘要 | 本论文通过模块化自组装设计多种具有特定功能基团修饰的平面型有机多齿配体和金属离子作为构筑单元，基于金属离子和多齿配体配位自组装原理，构筑具有特定几何形状和功能的纳米多维尺度超分子金属-配体容器化合物。具体研究内容主要包括设计并制备了油溶性M12L24型笼状截角立方八面体球、油溶性M6L4型笼状八面体球、水溶性M6L4型笼状八面体球以及油溶性M6L12型笼状正方体球，并对这些化合物进行了核磁、元素分析、原子力显微镜、透射电镜、紫外光谱、荧光光谱以及电化学等测试表征。同时，运用分子模型理论预测超分子体系的结构、能量和分子轨道。此外，我们还对这类笼状自组装超分子体系潜在的光电性质和分子识别功能进行了初步研究。主要内容包括以下几个方面：1．设计合成了分别含有光电活性基团（2-噻吩，3-噻吩基团）的M12L24型笼状截角立方八面体球，并对其结构进行了核磁、元素分析、AFM表征，研究了其电化学性质，实现了超分子多电子体系的构筑。2．通过在配体构筑单元外侧基连接功能活性分子（二茂铁基团或金刚烷基团），实现对M12L24型笼状截角立方八面体球的官能团化；优化了体系的分子结构，实验表明这些活性基团同时具有独特的电化学性质。3．设计并合成了侧基由二苯并-24-冠醚-8基团修饰的双齿配体并构筑了M12L24型笼状截角立方八面体球，对其结构进行了表征，该体系可能用来识别二级铵盐离子。4．设计并合成了两种油溶性M6L4型超分子笼状八面体球，通过核磁、元素分析、AFM表征了其结构和分子大小；通过分子模型理论计算得到了优化的分子结构和电子能级结构，电化学实验表明超分子体系具有新颖的电化学性质。5．通过水溶性M6L4型笼状八面体球对二茂铁基衍生物的包覆识别作用，测定了主体分子识别客体分子前后的电化学响应变化，研究了主客体体系对外界电压变化的电化学响应。6．设计、制备并表征了由咔唑基修饰的M6L12型笼状正方体球，通过分子模型理论获得了其优化的分子结构；通过紫外、荧光光谱分析结果表明该分子具有潜在的光电活性。 |
| 英文摘要 | In this thesis，we designed various functional organic ligands subunits and metal ions subunits. Through combining the metal ions subunits and organic ligands subunits by the modular self-assembled principles, we constructed well-defined, special geometrical metal-ligand container compounds, including various cages, such as oil soluble cubooctahedron M12L24 spheres, oil soluble octahedral M6L4 spheres, water soluble octahedral M6L4 spheres and oil soluble cube M6L12 spheres. The spherical complexes have been characterized by various characterization methods, including NMR spectroscopy, elemental analysis, AFM images, TEM images, UV and PL spectra and electrochemical experiments. The molecular dynamics modeling theory was employed to optimize the molecular structures and predict energy levels. The preliminary studies of photoelectric properties and recognition function were explored. The main content is as following:1. Two different thiophene functional groups (2-substituted or 3-substituted thiophene) were introduced and attached to the organic bidentate ligands, thus obtained functional M12L24 spheres. The spherical complexes have been characterized by NMR spectroscopy, elemental analysis, AFM images and electrochemical experiments. The thiophene units hanging outside of the spheres which would make the self-assembled coordination systems exhibit some multi-redox properties.2. We obtained the functional M12L24 complexes with attached some specific moieties. The coordination self-assembly allows for precise position control of 24 ferrocene or 24 adamantane functionalities. The molecular dynamics modeling theory was employed to optimize the molecular structures. The multi-redox molecules exhibited unique electrochemical properties.3. The nanosized M12L24 complex was obtained with 24 peripherally appended dibenzo[24]crown-8 (DB24C8) functional groups. The spherical complex was well characterized. Such functionalized sphere may host dialkylammonium ions to show potential applications in molecular recognition and sensors.4. We prepared two novel oil-soluble M6L4 octahedral assemblies through coordination self-assembly. The spherical complexes were characterized by NMR spectroscopy, elemental analysis, AFM images. The molecular dynamics modeling theory was employed to optimize the molecular structures and energy levels. Electrochemical experiments indicated that self-assembled complexes exhibited interesting multi-redox properties. 5. We constructed a functional host-guest system. The host was an octahedral M6L4 assemblies, which could bind ferrocenyl-substituted compounds as guest molecules. The cage and host-guest complexes were investigated by spectroscopy analysis and electrochemical studies. Meanwhile, upon exerting an electro-stimuli oxidative voltage, the host-guest systems were further investigated by electrochemical analysis.6. A functional M6L12 cube molecule with attached multiple carbazole-based moieties was obtained. The molecular dynamics modeling theory was employed to optimize the molecular structure. The UV and PL spectra of the cube were further explored, and it would be useful to design new type light-emitting devices. |
| 学科主题 | 先进功能有机材料 |
| 语种 | 中文 |
| 公开日期 | 2013-01-06 |
| 源URL | [http://ir.qibebt.ac.cn:8080/handle/337004/1441]  |
| 专题 | 青岛生物能源与过程研究所_先进有机功能材料团队 |
| 推荐引用方式 GB/T 7714 | 姜飞. 模块化自组装笼状超分子金属配合物的合成表征和性质研究[D]. 北京. 中国科学院研究生院. 2012. |
入库方式： OAI收割
来源：青岛生物能源与过程研究所
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