基于非手性芘的超分子手性圆偏振发光材料

Organic light-emitting materials with characteristics of circularly polarized luminescence have become a hot research at home and abroad, which have broad application prospects in the fields of optical information storage and processing, liquid crystal displays, etc. Introducing chiral groups to the light-emitting molecules are the effective methods to obtain circularly polarized luminescent materials, however, the reports about constructing the circularly polarized luminescence materials from achiral building blocks have not yet been found. To solve this problem, the project will be carried out with preparation of achiral linear and disc supramolecular complexes containing pyrene by means of ionic self-assemblied technology. Then the supramolecular complexes will exhibit chiral thermotropic liquid crystal behaviors through chemical tailoring, the relationship between temperature and polarized luminescence performance will be studied. Supramolecular chiral helical structures will be constructed by regulating the solvent environment of the achiral pyrene derivatives, the single chiral helical assemblies will be obtained through chiral introduction. The dynamic control of both aggregated structure and circularly polarized luminescence will be realized through adjusting pH, and the smart pH-responsive polarized luminescent materials will be developed. The project will develop a kind of novel circularly polarized luminescent materials containing pyrene, which will be extremely expected to have potential applications in the optoelectronic fields of chiral materials, the project will provide theoretical proof and experimental evidence for new methods of constructing circularly polarized luminescence materials.

具有圆偏振性质的有机发光材料在光信息存储与处理、液晶显示器等领域具有广阔的应用前景，已成为国内外研究的热点。获得圆偏振发光材料的有效方法是将手性基团引至发光分子中，然而目前尚未发现国内外有以非手性的研究对象构筑圆偏振发光材料的报道。针对这一问题，本项目将利用离子自组装方法制备线型及盘状结构的非手性芘超分子复合物；通过化学裁剪调节分子间作用力驱动复合材料具有手性热致液晶性质，以手性液晶为载体研究温度与圆偏振发光的关系；调控溶剂环境驱动非手性的芘组织成具有超分子手性的螺旋聚集体，并以手性诱导为途径制备单一手性的螺旋组装体；通过改变pH值实现聚集结构与偏振发光性能的动态调控，发展pH响应的智能型圆偏振发光材料。本项目将会构筑一类新颖的含芘的圆偏振发光材料，有望在手性发光等光电子领域具有实际价值，将为构筑圆偏振发光材料的新方法提供理论证明和实验依据。

超分子化学的快速发展拓宽了手性研究领域的范围，使手性材料的制备从传统的共价合成发展到利用超分子方法进行组装。获得圆偏振发光材料的有效方法是将发光基团引入到手性环境中，用光或电子激发螺旋排列的发光基团能产生圆偏振光发光现象。圆偏振发光材料的开发离不开超分子手性材料的设计与合成。本项目借助于非共价相互作用，以手性诱导为切入点，利用离子自组装方法使原本不具备手性的构筑基元表现出超分子手性信号。通过揭示超分子复合物的手性组装机理，进一步实现超分子组装体的手性功能化。基于以上的研究目标和思路，我们完成了如下工作: 1、通过设计合理的超分子组装方案，合成了一类新颖的含胆固醇基团的手性两亲分子，构筑了在室温下即表现出液晶性质的手性离子液晶材料。2、利用离子自组装方法构筑了含芘的超分子复合物，得到了含芘的手性发光离子液晶，实现了基于非手性芘的超分子手性圆偏振发光材料。3、以对称线型结构的非手性多金属氧簇为研究对象，实现了多金属氧簇的螺旋自组装。通过改变介电常数实现了螺旋组装体与花状聚集体体之间的调控。详细阐明了非手性多金属氧簇螺旋组装体的形成机理和结构演化过程。4、设计合成了一系列含多金属氧簇的手性超分子液晶材料，手性有机阳离子通过分子间静电相互作用诱导非手性的多金属氧簇表现出电荷数目可调的手性信号，这对手性纳米液晶的设计提供了新思路。5、通过2-吡啶甲醛苯腙锂与金属盐（Fe, Co, Ni, Zn, Sn, Zr）的反应构筑了以吡啶氮和苯氨基氮原子为配位原子的六元金属环配合物，其通过更进一步与二氯甲烷的偶联-异构化协同反应得到了碳桥联的双吡啶甲醛苯腙化合物。利用锆、钛过渡金属酰酮亚胺类配合物高效率地催化烯烃聚合。