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Helical Polyacetylenes Induced via Noncovalent Chiral Interactions and Their Applications as Chiral Materials

机译:通过非共价手性相互作用诱导的螺旋聚乙炔及其在手性材料中的应用

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摘要

Construction of predominantly one-handed helical polyacetylenes with a desired helix sense utilizing noncovalent chiral interactions with nonracemic chiral guest compounds based on a supramolecular approach is described. As with the conventional dynamic helical polymers possessing optically active pendant groups covalently bonded to the polymer chains, this noncovalent helicity induction system can show significant chiral amplification phenomena, in which the chiral information of the nonracemic guests can transfer with high cooperativity through noncovalent bonding interactions to induce an almost single-handed helical conformation in the polymer backbone. An intriguing “memory effect” of the induced macromolecular helicity is observed for some polyacetylenes, which means that the helical conformations induced in dynamic helical polyacetylene can be transformed into metastable static ones by tuning their helix-inversion barriers. Potential applications of helical polyacetylenes with controlled helix sense constructed by the “noncovalent helicity induction and/or memory effect” as chiral materials are also described.
机译:描述了基于超分子方法,利用与非外消旋手性客体化合物的非共价手性相互作用,构建具有所需螺旋感的主要单手螺旋聚乙炔。与具有共价键合到聚合物链上的光学活性侧基的常规动态螺旋聚合物一样,这种非共价螺旋诱导系统可以显示出明显的手性扩增现象,其中非外消旋客体的手性信息可以通过非共价键相互作用以高协同性转移至在聚合物主链中诱导几乎单手的螺旋构象。对于某些聚乙炔,观察到了一个诱人的大分子螺旋结构的“记忆效应”,这意味着可以通过调节它们的螺旋反转势垒,将动态螺旋聚乙炔中诱导的螺旋构象转化为亚稳态的静态构象。还描述了通过“非共价螺旋诱导和/或记忆效应”构建的具有受控螺旋感的螺旋聚乙炔作为手性材料的潜在应用。

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