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

螺旋液晶共轭聚合物的合成及手性发光材料的开发

• 批准号: 14205135
• 负责人: AKAGI Kazuo
• 金额: $ 35.44万
• 依托单位: University of Tsukuba
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (A)
• 财政年份: 2002
• 资助国家: 日本
• 起止时间: 2002 至 2005
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-14205135/
• 关键词: conjugated polymer; hierarchical structure; control of function; helical polyacetylene; chiral liquid crystal filed; helical structure; chiral luminescence; chiral dopant; 液晶性; 共役系高分子; キラルネマティック液晶; 光学活性; 直線偏光; 円偏光

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.

利用液晶的自发取向功能和外场响应功能，发展了π共轭聚合物的新合成方法，并通过控制聚合物的高阶结构，提出了新的功能。本研究的目的是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色性光学RGB荧光，开发具有线偏振和圆偏振发光的新型塑料光学材料.我们发展了以手性液晶为反应场的不对称聚合方法。本文采用化学聚合和电化学聚合的方法，不仅合成了螺旋聚乙炔，而且合成了具有多级螺旋结构的杂环和芳香族共轭聚合物。我们成功构建了分级螺旋形貌和圆偏振发光（手性发光）.通过在侧链型液晶聚对苯撑衍生物中引入手性化合物，构建了基于手性液晶的螺旋结构，实现了吸收和荧光的圆二色性。此外，通过对手性化合物进行化学修饰，合成了具有光、温响应功能的手性掺杂剂，并将其应用于先进的手性反应领域.我们合成了主链型液晶均聚物和共聚物，其均聚物和共聚物由侧链上的手性烷基取代的亚苯基和亚噻吩基组成，并获得了与链内螺旋扭曲和链间螺旋堆积相关的圆二色性发光。

项目成果

Synthesis and Properties of Helical Conjugated Polymers in Chiral Liquid Crystalline Filed

手性液晶场螺旋共轭聚合物的合成与性能

• 发表时间: 2006
• 期刊: Kagaku 61,3
• 作者: 田中幹樹;秋元博路;作増学美;久保昇三;K.Akagi
• 通讯作者: K.Akagi

S.Yorozuya: "Synthesis and Properties of Chiral Thienylene-Phenylene Copolymers"Synthetic Metals. (in press). (2003)

S.Yorozuya：“手性噻吩基-亚苯基共聚物的合成与性能”合成金属。

A.Akagi: "Nanoscience and Nanotechnology"Am. Sci. Pub. (in press). (2003)

A.Akagi：“纳米科学和纳米技术”Am。

A.Akagi: "The Chemical Society of Japan : 125 Years to the future"Metallic Luster of Polyacetylene Film Drawing Gold Medal of Nobel Prize (in press). (2003)

A.Akagi：《日本化学会：125年的未来》聚乙炔薄膜的金属光泽绘制诺贝尔奖金奖（出版中）。

Synthesis of Shish-Kebab-Type Liquid Crystalline Polyfluorene Derivatives

Shish-Kebab型液晶聚芴衍生物的合成

• 发表时间: 2003
• 期刊: Synthetic Metals 135-136・4
• 作者: Yajima;K.;Yamamoto;Y.;Maeji;I.;Kurosaki;T.;Yokota;T.;Sato;H.;Shibata;E.;S.J.Zheng
• 通讯作者: S.J.Zheng