The first optically active polycarbazoles
The first optically active polycarbazoles
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第一个光学活性聚咔唑
DOI：
10.1021/ma0344184
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发表时间：
2003
期刊：
影响因子：
5.5
通讯作者：
C. McKenna
中科院分区：
文献类型：
--
作者：
Zhongbiao Zhang;M. Motonaga;M. Fujiki;C. McKenna
天然存在的聚合物中高度有序的手性结构在决定其精确和复杂的生物化学功能方面起着重要作用。设计能够模拟生物聚合物手性识别特性的合成螺旋聚合物是目前人们关注的焦点。对映体分离、催化和传感是基于响应性三维分子内或分子间超手性结构的分子识别的最有前途的应用之一。1-8旋光性共轭聚合物9 -11代表了适用于此目的的一类有吸引力的手性大分子，因为它们的手性行为可以通过沿着主链共轭产生的非线性导电或光学性质12 -15来增强。在这篇通讯中，我们报道了光学活性聚咔唑的第一个例子。这些新型的手性π共轭聚合物在单个聚合物链内具有高度有序的手性骨架构象，但在它们的聚集体中具有手性链间π堆积结构。在聚集过程中，沿着沿着每个聚合物链的二级手性骨架构象的维持导致聚集体中的一种新型的高阶手性超结构，这表明光学活性聚咔唑将是开发和理解手性聚合物材料的有用工具。
The highly ordered chiral structures in naturally occurring polymers play a significant role in determining their precise and sophisticated biochemical functionalities. The design of synthetic helical polymers capable of emulating the chiral recognition properties of biopolymers is currently a focus of much interest. Enantioseparation, catalysis, and sensing are among the more promising applications of molecular recognition based on responsive three-dimensional intramolecular or intermolecular superchiral structures. 1-8 Optically active conjugated polymers9-11 represent an attractive class of chiral macromolecules adaptable to this purpose because their chiral behavior can be augmented by nonlinear electrically conductive or optical properties12-15 arising from conjugation along the backbone. In this Communication, we report the first example of optically active polycarbazoles. These novel chiral π-conjugated polymers are proposed to adopt a highly ordered chiral backbone conformation within a single polymer chain, but a chiral interchain π-stacking structure in their aggregates. The maintenance of the second-order chiral backbone conformation along each polymer chain during aggregation leads to a novel type of higher order chiral superstructure in the aggregates, suggesting that optically active polycarbazoles will be useful tools for developing and understanding chiral polymeric materials.