Synthesis of Helical Liquid Crystalline Conjugated Polymers and Development of Chiral Luminescent Materials

利用液晶的自发取向函数和外场响应函数，提出了合成π共轭聚合物的新方法，并通过控制聚合物的层次高阶结构提出了新的功能。在本研究中，我们旨在合成液晶和螺旋芳香共轭聚合物，并利用聚合物的液晶性和圆二向色光学RGB荧光，开发具有线偏振和圆偏振发光的创新型塑料光学材料。以手性液晶为反应场，发展了不对称聚合方法。我们不仅合成了螺旋型聚乙炔，还采用化学聚合和电化学聚合的方法合成了具有层次螺旋结构的杂环和芳香共轭聚合物。我们成功地构建了层次螺旋结构和圆极化发光（手性发光）。我们将手性化合物加入到侧链型液晶聚对苯衍生物中，构建了基于手性向列相液晶的螺旋结构，并实现了吸收和荧光的圆二色性。此外，我们还通过对手性化合物进行化学修饰，合成了具有光响应和温度响应功能的手性掺杂剂，并将其用于高级手性反应领域。我们合成了苯乙烯和乙烯基侧链上带有手性烷基取代基的主链型液晶均聚物和共聚物，并获得了与链内螺旋扭曲和链间螺旋堆积相关的圆二向色发光。

We developed novel synthetic methods for π-conjugated polymers by using both spontaneous orientation and external field-responsive functions of liquid crystal, and put forward new functions through control of hierarchical higher order structures of the polymers. In the present study, we aimed to synthesize liquid crystalline and helical aromatic conjugated polymers, and to develop innovative plastic optical materials with linearly and circularly polarized luminescence by virtue of liquid crystallinity and circular dichroic optical RGB fluorescence of the polymers.1. We developed asymmetric polymerization method on the basis of chiral liquid crystal as a reaction field. We synthesized not only helical polyacetylene but also heterocyclic and aromatic conjugated polymers with hierarchical spiral structures, by means of chemical and electrochemical polymerizations. We succeeded in constructing hierarchical spiral morphology and circularly polarized luminescence (chiral luminescence).2. We construct the helical structure based on chiral nematic liquid crystal by adding chiral compounds into side-chain type liquid crystalline poly-para-phenylene derivatives, and achieved to evolve circular dichroism in absorption and fluorescence. Besides, we synthesized chiral dopants with photo- and temperature-responsive functions through chemically modifications of chiral compounds, and used them for advanced chiral reaction field.3. We synthesized main-chain type liquid crystalline homopolymers and copolymers consisting of phenylene and thienylene moieties with chiral alkyl substituents in side chains, and obtained circularly dichroic luminescence associated with intra-chain helical twisting and inter-chain helical stacking.