Induced Circular Dichroism of Isotactic Poly(2-vinylpyridine) with Diverse and Tunable "Sergeants-and-Soldiers" Type Chiral Amplification
Induced Circular Dichroism of Isotactic Poly(2-vinylpyridine) with Diverse and Tunable "Sergeants-and-Soldiers" Type Chiral Amplification
复制标题
具有多样化且可调谐的“军士和士兵”型手性放大的全同立构聚（2-乙烯基吡啶）的诱导圆二色性
DOI：
10.1021/acsmacrolett.9b00216
复制
发表时间：
2019-07-01
影响因子：
7.015
通讯作者：
Wan, Xinhua
中科院分区：
文献类型：
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作者：
Yan, Zijia;Cai, Siliang;Wan, Xinhua
从非手性聚合物中方便高效地构建具有多种可调手性放大的螺旋结构是吸引人的，但在开发多功能材料方面仍然是一个挑战。本文报道了一种高等规聚(2-乙烯基吡啶)(99%)、(+)-樟脑磺酸和十二烷基苯磺酸的大分子酸碱络合物。在CHCl3及其与CH3CN的混合物中，通过吡啶基团和酸性离子之间的离子相互作用，手性添加剂的不对称诱导使聚合物主链沿择优方向扭曲。诱导圆二色谱的符号和强度取决于碱酸比、手性酸含量和溶剂性质。通过系统地调节溶剂组成，由于手性-手性和手性非手性离子对的溶剂依赖偏置，首次在一个体系中实现了四种不同类型的“中士和战士”模手性放大。
Facile and efficient construction of the helical structure with diverse and tunable chiral amplification from an achiral polymer is attractive but remains a challenge to develop multiple functional materials. We report herein a macromolecular acid base complex of highly isotactic poly(2-vinylpyridine) (mmmm > 99%), (+)-camphorsulfonic acid, and dodecylbenzensulfonic acid. The asymmetric induction of the chiral additive through the ionic interactions between pyridinium pendants and acid ions drives the polymer backbone to twist in a preferred direction in CHCl3 and its mixture with CH3CN. The sign and intensity of induced circular dichroism rely on the base to acid ratio, the chiral acid content, and the solvent nature. By systematically tuning the solvent composition, four distinct types of "sergeants-and-soldiers" mode chiral amplification are achieved for the first time within a single system owing to the solvent dependent bias of chiral-chiral and chiral achiral ion pairs.