苯并咪唑类衍生物超分子凝胶的制备及其发光性能研究

发布时间：2018-06-09 22:38

本文选题：苯并咪唑 + 软物质　；参考：《兰州大学》2015年博士论文

【摘要】：超分子凝胶作为一种软物质,由于其独特的结构和广泛的应用而成为近年来超分子化学和材料科学领域的研究热门；超分子凝胶在材料科学、液晶材料、智能材料、无机纳米材料、药物释放、固定霉、生物传感、发光材料等领域都有着潜在的应用价值。本文以苯并咪唑为母体,选取酰肼或酰胺为修饰官能团,合成了一系列凝胶因子,研究凝胶因子的自组装过程和发光性能；并且引入金属离子制备成金属凝胶,利用配体和金属离子的配位作用优化凝胶的发光性能。本论文包括以下五个部分：1.绪论。凝胶文献综述与本论文课题的提出,内容涉及凝胶的概念、分类、应用及表征方法、研究现状、存在挑战性课题。2.用酰肼功能化的苯并咪唑配体制备了一类具有双重响应性能的发绿光的水凝胶G1-gel。并且发现在该凝胶中加入硝酸铽之后,由于配体和Tb3+的配位作用使其绿光显著增强。另外,这种凝胶在凝胶态和干凝胶时的光谱截然不同。这类凝胶结构具有酸碱可逆性和热可逆性。这对制备多重响应性能的智能超分子凝胶具有指导意义。3.制备了一种双发光的酰腙功能化的苯并咪唑衍生物凝胶因子(G2)。该凝胶因子在乙二醇中可以形成具有热可逆性和绿光发射的超分子凝胶(G2-gel)；有趣的是,在该凝胶中植入等物质的量的Cd2+后,通过增强苯并咪唑部分的发光转变成一种发蓝光的金属凝胶(Cd@G2-gel), Cd2+在此起到了光转换开关作用。这个结果对设计发光凝胶具有一定的理论意义。4.合成了一类具有双重组装功能的凝胶因子(G3),该凝胶因子由西佛碱和苯并咪唑构成,在DMSO和乙二醇混合溶剂中的凝胶化行为具有显著的热响应性能。基于AIE(聚集诱导发光)效应,该凝胶因子可以在DMSO和乙二醇混合溶剂中形成一种蓝光发射的超分子凝胶(G3-gel)。当在其中加入Cd2+后,蓝光进一步增强。蓝光增强现象是由于分子内氢键和配体与金属离子的配位键的双重作用促使该分子的内部旋转极大地受到限制而引起的。5.基于前面四章凝胶因子的设计,设计了一种由一条柔性链连接两个苯并咪唑衍生物分子的凝胶因子(G4)。该凝胶因子在DMSO和乙二醇中形成一种发蓝光的超分子有机凝胶。有趣的是当向其中加入Y3+调控发光性能时,结果发现凝胶坍塌而只能得到溶液。但是把溶剂体系换成DMF和水混合溶剂后,可以制备出发强烈蓝光的金属凝胶。对该配合物做粉末衍射分析后发现,Y3+和配体G4形成的配合物是一种非晶态物质。
[Abstract]:As a kind of soft matter, supramolecular gel has become a hot research field in the field of supramolecular chemistry and material science in recent years because of its unique structure and wide application. Inorganic nanomaterials, drug release, fixed mold, biosensor, luminescent materials and other fields have potential application value. In this paper, a series of gel factors were synthesized with benzimidazole as parent and acyl hydrazide or amide as modified functional groups to study the self-assembly process and luminescence properties of gel factors, and metal ions were introduced to prepare metal gels. The luminescence properties of gels were optimized by the coordination of ligand and metal ions. This thesis includes the following five parts: 1. Introduction The review of gel literature and the subject of this paper are related to the concept, classification, application and characterization of gel. A class of green-emitting hydrogels G1-gelatin with double response properties were prepared by using benzimidazole ligands functionalized by acyl hydrazide. After adding terbium nitrate into the gel, the green light of TB _ 3 was significantly enhanced due to the coordination of the ligand and TB _ 3. In addition, the spectra of the gel in the gel state and in the xerogel are very different. This kind of gel structure has acid base reversibility and thermal reversibility. This has a guiding significance for the preparation of intelligent supramolecular gels with multiple response properties. A double luminescent acylhydrazone functionalized benzimidazole derivative gel factor G 2 O was prepared. The gel factor can form a supramolecular gel G2-geline with thermal reversibility and green light emission in ethylene glycol. Interestingly, the amount of CD _ 2 implanted in the gel is after the addition of CD _ 2. By enhancing the luminescence of the benzimidazole part, it is transformed into a blue metal gel, CDD @ G2-gelatin, in which CD2 acts as an optical switch. This result has certain theoretical significance for the design of luminescent gels. A kind of gelling factor G _ 3N with dual assembly function was synthesized. The gel factor is composed of Schiff base and benzimidazole. The gelation behavior in the mixed solvent of DMSO and ethylene glycol has remarkable thermal response. Based on the AIE (aggregation induced luminescence) effect, the gel factor can form a blue emitting supramolecular gel, G3-gelatin, in the mixed solvent of DMSO and ethylene glycol. When CD 2 was added, the blue light was further enhanced. The enhancement of blue light is caused by the double interaction of the intramolecular hydrogen bond and the coordination bond between the ligand and metal ions, which greatly restricts the internal rotation of the molecule. Based on the design of the gel factor in the previous four chapters, a gel factor G _ 4 is designed, which is connected by a flexible chain to two benzimidazole derivative molecules. The gel factor formed a blue-emitting supramolecular organic gel in DMSO and ethylene glycol. Interestingly, when Y3 was added to regulate luminescence, it was found that the gel collapsed and only solution was obtained. However, when the solvent system is replaced by DMF and water, the metal gels with strong blue light can be prepared. It was found that the complex formed by Y _ 3 and ligand G _ 4 was an amorphous substance by powder diffraction analysis.
【学位授予单位】：兰州大学
【学位级别】：博士
【学位授予年份】：2015
【分类号】：O648.17

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