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动态共价键介导的非手性液晶嵌段共聚物薄膜螺旋组装体中的颜色可切换圆偏振发光

Dynamic Covalent Bonds-Mediated Color-Switchable Circularly Polarized Luminescence in Helical Assemblies of Achiral Liquid Crystal Block Copolymer Films.

作者信息

Yuan Jianan, He Xiaojie, Chen Lianjie, Lu Xuemin, Lu Qinghua

机构信息

School of Chemistry and Chemical Engineering, Shanghai Key Laboratory of Electrical Insulation and Thermal Aging, Shanghai Jiao Tong University, Dongchuan Road no. 800, Shanghai, 200240, China.

School of Chemical Science and Technology, Tongji University, Siping Road No. 1239, Shanghai, 200092, China.

出版信息

Angew Chem Int Ed Engl. 2025 Jan 27;64(5):e202419924. doi: 10.1002/anie.202419924. Epub 2025 Jan 9.

Abstract

Circularly polarized luminescence (CPL) film attracted considerable attention in information storage and encryption, three-dimensional display, and chiral recognition. However, due to the limited molecular mobility within thin film, achieving a high asymmetry factor and non-contact modulation of CPL remain challenging. In this work, color-switchable homochiral CPL films with high luminescence asymmetry factor (g~0.11) were constructed based on the co-assembly of a liquid crystal block copolymer (poly (ethylene oxide)-b-poly (methyl methacrylate) bearing cyanostilbene group) with axial chiral dinaphthalene diamine derivatives (R/S-DINBPA). Mechanistic investigation revealed that the efficient stacking of R/S-DINBPA with cyanostilbene groups and the liquid crystal field provide the driving force for chiral transfer and amplification. The dynamic covalent bonds of the cyanostilbene groups endow the film with chiral fixation ability and enable precise modulation of CPL luminescence bands under UV light irradiation, making it suitable for chiral patterned anti-counterfeit encryption. This facile strategy provides a general platform for designing intelligent chiroptical materials.

摘要

圆偏振发光(CPL)薄膜在信息存储与加密、三维显示及手性识别方面备受关注。然而,由于薄膜内部分子迁移率有限,实现高不对称因子和CPL的非接触调制仍具有挑战性。在这项工作中,基于液晶嵌段共聚物(带有氰基芪基团的聚环氧乙烷-b-聚甲基丙烯酸甲酯)与轴向手性二萘二胺衍生物(R/S-DINBPA)的共组装,构建了具有高发光不对称因子(g~0.11)的颜色可切换同手性CPL薄膜。机理研究表明,R/S-DINBPA与氰基芪基团的有效堆积以及液晶场为手性转移和放大提供了驱动力。氰基芪基团的动态共价键赋予薄膜手性固定能力,并能在紫外光照射下精确调制CPL发光带,使其适用于手性图案防伪加密。这种简便策略为设计智能手性光学材料提供了一个通用平台。

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