Helical Assemblies of One-Dimensional Supramolecular Polymers Composed of Helical Macromolecules: Generation of Circularly Polarized Light Using an Infinitesimal Chiral Source,Journal of the American Chemical Society

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Helical Assemblies of One-Dimensional Supramolecular Polymers Composed of Helical Macromolecules: Generation of Circularly Polarized Light Using an Infinitesimal Chiral Source
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2020-01-27 , DOI: 10.1021/jacs.9b13584
Tomoyuki Ikai _{1,

2} , Mitsuhiro Okubo ₁ , Yuya Wada ₁

Affiliation

We report the synthesis of one-dimensional supramolecular polymers composed of one-handed helical macromolecules bearing fluorescent pendant groups, and the generation of circularly polarized light based on hierarchical chiral amplification starting from a tiny amount of chiral substituent. Copolymerization of benzo[1,2-b:4,5-b']dithiophene-appended achiral/chiral isocyanides (99:1, mol/mol) with a solid-state photoluminescence feature afforded sub-micrometer supramolecular fibers, in which almost perfect single-handed helical polyisocyanides were noncovalently connected end-to-end. The resulting helical supramolecular polymers were further helically assembled to form a cholesteric liquid crystal film with an intense circularly polarized luminescence (CPL) signal. Surprisingly, the supramolecular system containing only 0.01 mol% of the chiral monomer unit also emitted the observable circularly polarized light owing to multiple chiral amplification from an infinitesimal point chirality to helical chirality, and then to supramolecular chirality. Furthermore, chiral information was efficiently transferred from the helically assembled supramolecular system containing 1 mol% of the chiral unit to achiral dye molecules blended in the film, allowing full-color tunable induced CPL with luminescence dissymmetry factors greater than 1.0 × 10-2. This unprecedentedly strong chiral amplification enables the creation of helical supramolecular polymers and chirally assembled systems with various chiral functions based solely on an infinitesimal chiral source.

中文翻译：

由螺旋大分子组成的一维超分子聚合物的螺旋组装：使用无穷小手性源产生圆偏振光

我们报告了由带有荧光侧基的单手螺旋大分子组成的一维超分子聚合物的合成，以及基于从少量手性取代基开始的分级手性放大的圆偏振光的产生。具有固态光致发光特征的苯并[1,2-b:4,5-b']二噻吩附加的非手性/手性异氰化物（99:1，mol/mol）共聚得到亚微米超分子纤维，其中几乎完美的单手螺旋聚异氰化物是端对端非共价连接的。得到的螺旋超分子聚合物进一步螺旋组装形成具有强烈圆偏振发光（CPL）信号的胆甾型液晶薄膜。令人惊讶的是，超分子系统仅包含 0。由于从无穷小的点手性到螺旋手性，再到超分子手性的多重手性放大，01 mol%的手性单体单元也发射了可观察到的圆偏振光。此外，手性信息从包含 1 mol% 手性单元的螺旋组装超分子系统有效地转移到混合在薄膜中的非手性染料分子，允许全色可调诱导 CPL，发光不对称因子大于 1.0 × 10-2。这种前所未有的强手性放大能够创建螺旋超分子聚合物和具有各种手性功能的手性组装系统，仅基于无穷小的手性源。

更新日期：2020-01-27

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