有序卟啉复合薄膜的自导向组装及其性能研究

发布时间：2019-06-06 17:00

【摘要】：三维金属有机骨架材料(MOFs)薄膜的微结构、组装方式及方法直接影响其性能。因此,如何设计结构单元并通过简单的过程构筑稳定且性能优异的三维有序薄膜成为该领域重点研究的方向之一。金属卟啉的结构易于调制而且具有较高的热稳定性和化学稳定性,在光电器件、催化和分子识别等领域都有广泛应用。因此,以金属卟啉分子作为结构单元构建MOFs薄膜,能更加精细地调控MOFs薄膜的结构并丰富其性能。在本论文中,我们设计、合成了一种能在三维方向自导向组装的笼形倍半硅氧烷修饰的新型卟啉钴单体。利用卟啉单体自身的结构特点,经共轭双齿桥联配体诱导,促使单体定向排列并在三维方向上自导向组装,构筑了多种稳定、有序的卟啉复合物薄膜,进而研究了其结构和光电性能之间的关系。主要研究内容如下：通过在反应过程中引入氧气,对Alder-Longo法进行改进,简单快速地制备了四羧基苯基卟啉及四羧基苯基卟啉钴配合物。利用紫外光谱、红外光谱、质谱等手段对产物进行了表征。将四羧基苯基卟啉钴分别酰氯化、硅烷化,合成出具有轴向配位能力(卟啉环中心带有钴离子)和水平方向水解-聚合能力(卟啉周边带有硅氧烷)的新型卟啉单体,利用紫外、红外、核磁等多种手段对所得产物进行了表征。利用4,4'-联吡啶诱导硅烷化的卟啉钴单体定向排列,以促进单体问以配位键(轴向,卟啉环中心的钻离子与桥联配体配位)和共价键(水平方向,卟啉周边硅氧烷的水解-聚合)为主要推动力进行自导向组装快速构筑了稳定、高光电活性的卟啉MOFs薄膜。利用小角X射线衍射、比表面积分析、热重分析、原子力显微镜、透射电镜、电化学等手段对该复合薄膜的微观结构、形貌和光电性能进行了表征和分析。结果表明：得到的卟啉MOFs薄膜具有介孔结构,水平方向C-Si-O-Si-C网络作为光学非活性的间隔基,减小了卟啉的堆积密度和分子之间直接的相互作用,使卟啉MOFs薄膜具有较高的耐热性。4,4'-联吡啶与卟啉环中心的钴离子的轴向配位保证了卟啉单体在轴向上有序组装,同时有效促进了电子转移,使获得的有序卟啉MOFs薄膜具有更高的光电响应和稳定性。分别以4,4'-联吡啶,吡啶炔,吡啶基卟啉作为双齿桥连配体,自导向组装了三种有序的卟啉MOFs薄膜。通过系统地结构表征和性能测试,详细研究了配体的种类、分子长度、共轭性能和稳定性等对卟啉MOFs薄膜的微观结构、形貌和光电性能的影响。
[Abstract]:The microstructure, assembly method and method of 3D organometallic skeleton material (MOFs) film directly affect its properties. Therefore, how to design structural units and construct stable and excellent three-dimensional ordered thin films through a simple process has become one of the key research directions in this field. Metalloporphyrins are easy to modulate and have high thermal and chemical stability. Metalloporphyrins are widely used in optoelectronic devices, catalysis and molecular recognition. Therefore, the construction of MOFs thin films with metalloporphyrins as structural units can regulate the structure of MOFs thin films more precisely and enrich their properties. In this thesis, we designed and synthesized a novel cobalt porphyrin monomer modified by cage silsesquioxane, which can be self-directed assembled in three dimensional direction. Based on the structural characteristics of porphyrin monomers and induced by conjugated double tooth bridged ligands, the monomers were arranged directionally and assembled in three dimensional direction, and a variety of stable and ordered porphyrin complex films were constructed. Furthermore, the relationship between its structure and optoelectronic properties is studied. The main research contents are as follows: the Alder-Longo method was improved by introducing oxygen into the reaction process, and the cobalt complexes of tetracarboxylphenyl porphyrin and tetracarboxylphenyl porphyrin were prepared simply and rapidly. The products were characterized by UV, IR and MS. A new type of porphyrin monomer with axial coordination ability (cobalt ion in the center of porphyrin ring) and horizontal hydrolysis-polymerization ability (with siloxane around the porphyrin) was synthesized by acyl chlorination and silanization of cobalt tetracarboxylphenyl porphyrin, respectively. The products were characterized by UV, IR, NMR and so on. In order to promote the coordination bond (axial, the drilling ion at the center of the porphyrin ring with the bridged ligand) and the covalent bond (horizontal direction), 4, 4 bipyridine induced directional arrangement of cobalt porphyrin monomers induced by silanization of cobalt porphyrin monomers in order to promote the coordination bond (axial, the drilling ion at the center of the porphyrin ring coordinate with the bridged ligand), Stable and highly photoactive porphyrin MOFs thin films were constructed rapidly by self-directed assembly with the main driving force of hydrolysis-polymerization of sioxane around porphyrins. The microstructure, morphology and photoelectric properties of the composite film were characterized and analyzed by small angle X-ray diffraction, specific surface area analysis, thermogravimetric analysis, atomic force microscope, transmission electron microscope and electrochemistry. The results show that the porphyrin MOFs thin films have mesoporous structure, and the horizontal direction C-Si-O-Si-C network is used as the optically inactivated spacer, which reduces the stacking density of the porphyrin and the direct interaction between the molecules. The MOFs thin films have high heat resistance. 4, the axial coordination of 4 渭 bipyridine with cobalt ions in the center of the porphyrin ring ensures the orderly assembly of the porphyrin monomers in the axial direction, and at the same time effectively promotes the electron transfer. The ordered porphyrin MOFs thin films have higher photoelectric response and stability. Using 4, 4 bipyridine, pyridine acetylene and pyridine porphyrins as double dentate bridged ligands, three ordered porphyrin MOFs thin films were self-directed. The effects of ligands, molecular length, conjugated properties and stability on the microstructure, morphology and optoelectronic properties of Porphyrins MOFs thin films were studied in detail by means of structural characterization and performance tests.
【学位授予单位】：上海应用技术学院
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：TB383.2

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