State Key Laboratory of Chemical Resource Engineering, College of Materials Science and Engineering, Beijing University of Chemical Technology, Beijing, 100029, China.
Synthetic Resin Laboratory, Petrochemical Research Institute, Petro China, Beijing, 102206, China.
Macromol Rapid Commun. 2022 Jun;43(11):e2200111. doi: 10.1002/marc.202200111. Epub 2022 Apr 25.
Polymer-based circularly polarized luminescent (CPL) materials have attracted ever-increasing interest. However, to construct CPL materials from achiral monomers is still a big challenge. Here, a series of chiral helical substituted polyacetylenes are prepared by helix-sense-selective polymerization (HSSP) of achiral acetylenic monomers (achiral monomer + fluorescent monomer). HSSPs are accomplished in a bi-solvent mixture consisting of chloroform and chiral α-pinene (chiral component). Chirality transfers from the chiral component to the helical copolymers during polymerization, thereby endowing the copolymers with helical chirality. The resulting copolymers are then fabricated into blend films which exhibit intense optical activity and CPL. The monomer ratio and the physical state of the copolymers have significant impacts on their chiroptical and CPL properties. The maximum luminescence dissymmetry factor of the blend films can be up to 1.3 × 10 . The universality of the established strategy for exploring polymer-based CPL materials is demonstrated by using different achiral fluorescent monomers. The present work opens a novel alternative for developing CPL-active polymeric materials starting from achiral monomers.
基于聚合物的圆偏振发光（CPL）材料引起了越来越多的关注。然而，从手性单体构建 CPL 材料仍然是一个巨大的挑战。在这里，通过手性单体（手性单体+荧光单体）的螺旋选择性聚合（HSSP）制备了一系列手性螺旋取代的聚乙炔。HSSP 在由氯仿和手性 α-蒎烯（手性组分）组成的双溶剂混合物中进行。在聚合过程中，手性从手性组分传递到螺旋共聚物，从而赋予共聚物螺旋手性。然后将得到的共聚物制成混合膜，其表现出强烈的光学活性和 CPL。共聚物的单体比和物理状态对其手性和 CPL 性质有显著影响。混合膜的最大发光不对称因子可达 1.3×10-3。通过使用不同的手性荧光单体，证明了所建立的探索基于聚合物的 CPL 材料的策略具有普遍性。本工作为从手性单体开发 CPL 活性聚合物材料开辟了一种新的选择。
