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含手性三联苯腰接型液晶聚乙炔的合成及其“甲壳效应”

谌烈1,孔欢玲1,陈义旺1,2*,李璠1   

  1. (1.南昌大学高分子研究所 南昌 330031;2.南昌大学化学系 南昌 330031)
  • 收稿日期:2011-12-12 修回日期:2012-01-18 出版日期:2012-11-10 发布日期:2012-11-10
  • 通讯作者: 陈义旺，教授; Tel/Fax:0791-83969561; E-mail:ywchen@ncu.edu.cn; 研究方向：功能高分子
  • 基金资助:
    国家自然科学基金（51073076,51003045）资助项目

Synthesis of Liquid Crystalline Polyacetylene Containing Chiral Terphenyl and Its “Jacket Effect”

CHEN Lie1, KONG Huanling1, CHEN Yiwang1,2*, LI Fan1   

  1. (1.Institute of Polymers,Nanchang University,Nanchang 330031,China;
    2.Department of Chemistry,Nanchang University,Nanchang 330031,China)
  • Received:2011-12-12 Revised:2012-01-18 Published:2012-11-10 Online:2012-11-10
  • Contact: Chen

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摘要： 设计、合成了一种新单体，并由[Rh(nbd)Cl]2/Et3N(nbd=2,5-降冰片二烯)催化聚合反应制备了一种具有较高相对分子质量(质均相对分子质量为30300)的含手性三联苯液晶聚乙炔PAM3OCO(TPh)(OR*)2{—[(CH=C(CH2)3OCO—terphenyl(OR*)2]n—,R*=(S)-2-甲基丁基}。 由于手性基团和三联苯液晶基元的引入，单体具有互变手性近晶C相，而聚合物则呈现互变的手性近晶A相液晶行为。 三联苯液晶基元以重心位置连接于聚合物主链并围绕主链所产生的“甲壳效应”赋予了聚合物很高的热稳定性（356 ℃）、发光性能和聚集诱导增强发光特性。 其薄膜状态下的发光强度明显大于其在稀溶液状态下的发光强度，且内量子效率和外量子效率分别为0.214和0.023。 紫外光激发下，聚合物在液晶状态下的发光强度明显优于溶液和薄膜状态，并且发光谱带发生了红移。

关键词: 聚乙炔, 液晶, 手性, 发光性能, &, ldquo, 甲壳效应&, rdquo

Abstract: A monomer has been designed, synthesized and polymerized with [Rh(nbd)Cl]2-Et3N(nbd:2,5-norbonadien) catalyst. The liquid crystalline polyacetylene bearing chiral terphenyl mesogen {—[(CH=C(CH2)3OCO—terphenyl(OR*)2]n—, R*=(S)-2-methylbutyl, (PAM3OCO(TPh)(OR*)2)} was obtained in high molecular mass(mass-average relative molecular mass is 30300). The monomer shows enantiotropic smectic C(SmC*) phase by introducing chiral groups and terphenyl mesogen, while its corresponding polymer exhibits enantiotropic smectic A(SmA*) liquid crystalline behavior. The “jacket effect” induced by the terphenyl mesogen linked at mass center position endows the polymer with high thermal stability(356 ℃), high photoluminescence and aggregationinduced emission enhancement(AIEE). Upon UV irradiation, the light-emitting of the solid state of the polymer fabricated at room temperature is stronger than that of the dilute solution, and its internal quantum efficiency and external quantum efficiency are 0.214 and 0.023, respectively. Photoluminescence of the polymer quenched from the liquid crystalline state of is obviously stronger and red-shifted than those of the solution and thin film states under excitation at the ultraviolet wavelength.

Key words: Polyacetylene, Liquid crystal, Chirality, Photoluminescence, &, ldquo, Jacket effect&, rdquo

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