Department of Polymer Chemistry, Kyoto University, Katsura, Kyoto 615-8510, Japan.
J Am Chem Soc. 2012 Dec 5;134(48):19795-807. doi: 10.1021/ja3086565. Epub 2012 Nov 27.
We synthesized disubstituted liquid crystalline polyacetylene (diLCPA) derivatives bearing 4-nonyloxy phenyl groups with lyotropic and thermotropic LC behavior. The poly(diphenylacetylene) main chain structure of the diLCPAs and the chirality induced with either chiral moieties or chiral dopants allow the formation of a highly ordered lyotropic N*-LC phase. Circular dichroism (CD) spectra of the diLCPAs imply that one-handed intrachain helical structures are formed in solution, while interchain helical π-stacking between the polymer main chains are formed in cast film and in the N*-LC state. Absorption dissymmetry factors (g(abs)) in the N*-LC state show values on the order of 10(-1). The N*-LC state facilitates the formation of helically π-stacked structures with a high degree of helical ordering of the diLCPA and is indispensable for the generation of circularly polarized luminescence (CPL) with high emission dissymmetry factors (g(em)) on the order of 10(-1). To the best of our knowledge, this is the highest reported value of CPL achieved for aliphatic, conjugated polymers. As an alternative to the thermotropic N*-LC phase, we have found that the lyotropic N*-LC phase of diLCPA could be promising materials possessing CPL functionality for use in next-generation π-conjugated organic optoelectronic devices, displays, and sensors.
我们合成了具有溶致和热致液晶行为的带有 4-壬氧基苯基基团的取代液晶聚乙炔(diLCPA)衍生物。diLCPAs 的聚二苯乙炔主链结构以及手性部分或手性掺杂剂诱导的手性允许形成高度有序的溶致 N*-LC 相。diLCPAs 的圆二色性(CD)谱表明,在溶液中形成了单链内螺旋结构,而在铸膜和 N*-LC 状态下,聚合物主链之间形成了螺旋 π-堆积。在 N*-LC 状态下的吸收不对称因子(g(abs))的值约为 10(-1)。N*-LC 态有利于形成具有高度螺旋有序的 diLCPA 的螺旋 π-堆积结构,并且对于产生具有约 10(-1)的高发射不对称因子(g(em))的圆偏振发光(CPL)是必不可少的。据我们所知,这是报道的脂肪族共轭聚合物中 CPL 的最高值。作为热致 N*-LC 相的替代物,我们发现 diLCPA 的溶致 N*-LC 相可能是具有 CPL 功能的有前途的材料,可用于下一代 π 共轭有机光电设备、显示器和传感器。