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宏观手性液晶量子点实现的自组装螺旋超结构中的增强型不对称圆偏振发光

Enhanced Asymmetric Circularly Polarized Luminescence in Self-Organized Helical Superstructures Enabled by Macro-Chiral Liquid Crystal Quantum Dots.

作者信息

Yu Huanan, Zhang Kaige, Yu Qiqi, Zhang Jingji, Ye Yongchun, Redshaw Carl, Chen Zhonghui, Xu Dongdong, Mehl Georg H

机构信息

School of Materials and Chemistry, China Jiliang University, Hangzhou 310018, China.

Key Laboratory of Organosilicon Chemistry and Materials Technology of Ministry of Education, College of Material, Chemistry, and Chemical Engineering, Hangzhou Normal University, Hangzhou 311121, China.

出版信息

ACS Nano. 2024 Nov 19;18(46):32056-32064. doi: 10.1021/acsnano.4c10423. Epub 2024 Nov 4.

Abstract

Circularly polarized luminescent (CPL) materials have garnered considerable interest for a variety of advanced optical applications including 3D imaging, data encryption, and asymmetric catalysis. However, the development of high-performance CPL has been hindered by the absence of simple synthetic methods for chiral luminescent emitters that exhibit both high quantum yields and dissymmetry factors. In this study, we present an innovative approach for the synthesis of macro-chiral liquid crystal quantum dots (Ch-QDs/LC) and their CPL performance enhancement through doping with 4-cyano-4'-pentylbiphenyl (5CB), thus yielding a CPL-emitting generator (CEG). The Ch-QDs/LCs were synthesized, and their surfaces functionalized with a chiral mesogenic ligand, specifically cholesteryl benzoate, anchored via a lipoic acid linker. Under the regulation of chiral 2S-Zn coordination complexes, the chiral LC encapsulation process promotes coordinated ligand substitution, resulting in an exceptional quantum yield of 56.3%. This is accompanied by high absorption dissymmetry factor () and luminescence dissymmetry factor () values ranging from 10 to 10, surpassing most reported dissymmetry factors by at least an order of magnitude. The modular Ch-QDs/LCs demonstrate the ability to transfer chirality to the surrounding medium efficiently and manifest macro-chiral characteristics within a nematic LC matrix. Utilizing Ch-QDs/LC as an effective CPL emitter within achiral 5CB matrices enabled the system to achieve a maximum value of 0.35. The resultant CEG device acted as a direct CPL source, initiating enantioselective photopolymerization.

摘要

圆偏振发光(CPL)材料因其在包括3D成像、数据加密和不对称催化等各种先进光学应用中的潜力而备受关注。然而,高性能CPL的发展受到了限制,因为缺乏一种简单的合成方法来制备具有高量子产率和不对称因子的手性发光体。在本研究中,我们提出了一种创新方法,用于合成宏观手性液晶量子点(Ch-QDs/LC),并通过掺杂4-氰基-4'-戊基联苯(5CB)来增强其CPL性能,从而得到一种CPL发射发生器(CEG)。合成了Ch-QDs/LC,并通过硫辛酸连接子将其表面用手性介晶配体(具体为胆固醇苯甲酸酯)进行功能化修饰。在手性2S-Zn配位络合物的调控下,手性液晶封装过程促进了配位配体的取代,从而实现了高达56.3%的优异量子产率。同时,其吸收不对称因子()和发光不对称因子()的值在10到10之间,比大多数已报道的不对称因子至少高出一个数量级。模块化的Ch-QDs/LC展示了将手性有效地传递到周围介质中的能力,并在向列型液晶基质中表现出宏观手性特征。在非手性5CB基质中利用Ch-QDs/LC作为有效的CPL发射体,使得该系统能够实现高达0.35的最大值。所得的CEG器件作为直接的CPL源,引发了对映选择性光聚合反应。

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