基于苯并噻二唑和三唑单元的Polycatenar化合物的合成及其自组装行为研究

发布时间：2018-09-16 21:55

【摘要】：液晶是有序性和流动性统一的超分子体系,是良好的自组装分子材料,因其具有自愈性、自适应性和刺激响应性。2,1,3-苯并噻二唑类化合物具有优异的光电性能,在有机光电领域广泛应用。液晶的形成能改善2,1,3-苯并噻二唑类化合物的光电性质。Click反应得到三唑基团在软物质材料设计中有重大优势。所以基于2,1,3-苯并噻二唑和三唑单元的液晶自组装及光电性质研究成为了现在研究的热点。第一章为文献综述部分,首先介绍了近几年2,1,3-苯并噻二唑类液晶的研究进展,主要综述了含一个(对称与不对称)或两个苯并噻二唑液晶化合物的研究。其次介绍有机超分子凝胶的研究。然后总结了含三唑单元的化合物对各种金属离子的识别研究。由于苯并噻二唑液晶分子形状以棒状和盘状居多,所以在苯并噻二唑类化合物中引入Polycantenar的分子设计概念,最后对Polycantenar液晶化合物做了简单的介绍。第二章介绍了基于苯并噻二唑和三唑的一代Polycantenar化合物的合成,光电性质及自组装性能研究。本章以Suzuki偶联反应和Click偶联反应为关键步骤合成了一系列以苯并噻二唑为核,三唑为中间连接基团,外围含六条烷氧基侧链的Polycantenar化合物BTDTr3Cn (BTD-苯并噻二唑,Tr-三唑,3Cn代表一边各含烷基链条数及烷基链长度),并通过POM, DSC和XRD对化合物的液晶自组装结构进行研究,结果表明：该系列化合物能形成Oblique柱相液晶,随着烷基链的增加,该系列化合物清亮点变化不大,熔点不断升高。该系列化合物在溶剂中形成有机凝胶,通过SEM观察到凝胶状态下的纤维管束自组装结构。经过光谱测试,发现该系列化合物具有较高的荧光量子量和很大的Stokes位移,这显示了该化合物优异光电性质的潜在应用。进行了离子识别研究后发现在DMSO: DCM(v/v)(2/1)中对Li+有较强的荧光吸收,说明了该系列化合物对Li+有较大离子选择性响应,可以作为化学传感器。最后得出结论该系列化合物可以作为多功能材料。第三章介绍了基于苯并噻二唑和三唑的二代树枝状Polycantenar化合物的合成及自组装性能研究。以Suzuki偶联反应和二次Click偶联反应为关键步骤合成了以苯并噻二唑为核,三唑为中间连接基团,外围含十二条十二烷氧基侧链的树枝状Polycantenar化合物BTDTr6C12,并通过POM, DSC和XRD测试了该化合物液晶自组装研究,结果表明：这个化合物形成了具有复杂Pm3n晶格群结构的胶束立方相。化合物在各种溶剂中能形成凝胶。通过SEM观察到化合物在凝胶状态下的纤维管束结构的自组装。然而尺寸和长度都较一代化合物更小。光电性质初步测量与一代化合物保持一致,并没有进一步的测量。第四章为实验部分,详细介绍了两类化合物的合成及其每个化合物相应的核磁共振谱图数据。
[Abstract]:Liquid crystal is a supramolecular system with uniform order and fluidity, and it is a good self-assembled molecular material. Because of its self-healing, adaptability and stimulative response, liquid crystal has excellent photoelectric properties. It is widely used in the field of organic photoelectricity. The formation of liquid crystal can improve the photoelectricity properties of 2O1C 3- benzothiadiazole compounds. Click reaction shows that triazole groups have great advantages in the design of soft matter materials. Therefore, the study of liquid crystal self-assembly and optoelectronic properties based on 2C-1, 3-benzothiadiazole and triazole units has become a hot topic. The first chapter is the literature review. Firstly, the recent progress in the study of the liquid crystals containing one (symmetric and asymmetric) or two benzothiadiazole liquid crystals is reviewed. Secondly, the study of organic supramolecular gel is introduced. The recognition of various metal ions by triazole-containing compounds was summarized. Because the molecular shapes of benzothiadiazole liquid crystals are mostly rod-like and disk-shaped, the molecular design concept of Polycantenar is introduced into the benzo-thiadiazole compounds. Finally, the Polycantenar liquid crystal compounds are briefly introduced. In chapter 2, the synthesis, photoelectric properties and self-assembly properties of a generation of Polycantenar compounds based on benzothiadiazole and triazole are introduced. In this chapter, a series of benzothiadiazole as nucleus and triazole as intermediate junction group were synthesized by using Suzuki coupling reaction and Click coupling reaction as the key steps. Polycantenar compound BTDTr3Cn (BTD- benzothiadiazolium Tr-triazolium 3Cn represents the number of alkyl chains and the length of alkyl chains in each side) was used to study the self-assembly structure of the compounds by POM, DSC and XRD. The results show that this series of compounds can form Oblique columnar liquid crystal. With the increase of alkyl chain, the bright spots of the series compounds change little and the melting point increases. This series of compounds form organic gels in solvents. Self-assembly structures of fiber bundles in the gel state are observed by SEM. It is found that this series of compounds have high fluorescence quantum quantity and large Stokes shift, which indicates the potential applications of the compounds in their excellent photoelectric properties. It was found that the fluorescence absorption of Li was strong in DMSO: DCM (v / v (2 / 1), which indicated that this series of compounds had a large ion-selective response to Li and could be used as a chemical sensor. Finally, it is concluded that this series of compounds can be used as multifunctional materials. In chapter 3, the synthesis and self-assembly properties of second generation dendritic Polycantenar compounds based on benzothiadiazole and triazole are introduced. The key steps of Suzuki coupling reaction and secondary Click coupling reaction were used to synthesize benzothiadiazole as nucleus and triazole as intermediate junction group. The dendritic Polycantenar compound BTDTr6C12, with 12 dodecoxy side chains was found to form a micellar cubic phase with complex Pm3n lattice group structure. The self-assembly of the compound was measured by POM, DSC and XRD. Compounds form gels in various solvents. The self-assembly of the fiber bundle structure of the compound in gel state was observed by SEM. However, both the size and the length of the compound are smaller than those of the first generation. The preliminary measurement of photoelectric properties is consistent with that of a generation of compounds, and no further measurements have been made. The fourth chapter is the experimental part. The synthesis of two kinds of compounds and the corresponding NMR data of each compound are introduced in detail.
【学位授予单位】：云南大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O626.2

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