基于L/D-赖氨酸盐酸盐和光活化AIE分子共组装实现圆偏振发光及动态调控
收稿日期: 2022-01-10
网络出版日期: 2022-03-10
基金资助
上海市科技创新行动计划扬帆项目(20YF1432400); 国家自然科学基金(22105128)
Circularly Polarized Luminescence and Dynamic Regulation Based on the co-Assembly of L/D-Lysine Hydrochloride and Photoactivated AIE Molecules
Received date: 2022-01-10
Online published: 2022-03-10
Supported by
Shanghai Sailing Program(20YF1432400); partially from the National Natural Science Foundation of China(22105128)
近年来, 基于分子组装产生圆偏振发光(CPL)的有机手性材料得到了迅猛的发展. 然而, 目前有机材料体系的CPL信号整体仍然较弱, 且缺乏精准的调控手段. 为此, 本工作以具有光活性的聚集诱导荧光增强(AIE)性质的多硫苯基化合物(M-1)为荧光染料, 以手性氨基酸L/D-赖氨酸盐酸盐(L/D-Lys)为手性模板, 通过分子间氢键作用, 在N,N-二甲基甲酰胺(DMF)/H2O的混合溶剂中形成超分子L/D-Lys@M-1共组装体. 共组装体在不良溶剂水的溶剂作用下诱导产生CPL, 且在紫外光激发下具有自聚集效应, 产生持续增强的荧光发射和圆二色(CD)信号. 通过荧光光谱、紫外吸收光谱和动态光散射(DLS)对组装体在光激发下的结构和光物理性质进行表征, 利用CD光谱以及CPL光谱等对基态和激发态手性性质进行研究. 结果表明, 在溶剂诱导和光激发下实现了L/D-Lys@M-1组装体的手性传递和放大, 且不对称因子(|glum|)达到了0.3×10-2. 该研究策略为非手性的荧光分子构建CPL体系及动态调控提供了策略.
关键词： 手性组装; 超分子; 光控; 圆偏振发光(CPL)
冯锡成 , 朱亮亮 , 岳兵兵 . 基于L/D-赖氨酸盐酸盐和光活化AIE分子共组装实现圆偏振发光及动态调控[J]. 化学学报, 2022 , 80(5) : 647 -651 . DOI: 10.6023/A22010015
In recent years, chiral materials based on circularly polarized luminescence (CPL) generated by molecular assembly have developed rapidly. However, the overall CPL signal of organic material systems is still weak and lacks precise modulation means. As a non-contact external stimulus, light stimulation has the advantages of precision and speed. Therefore, in this work, hexathiobenzene (M-1) with photoactive aggregation-induced emission (AIE) properties were used as fluorescent dyes, and chiral amino acids L/D-Lysine hydrochloride (L/D-Lys) were used as chiral templates. Supramolecular L/D-Lys@M-1 components are formed by intermolecular hydrogen bonding in a mixed solvent (N,N-dimethylformamide (DMF)/H2O). Specifically, 1 mmol/L M-1 and 6 mmol/L L/D-Lys were dissolved in 700 μL DMF. Next, add 300 μL ultra-pure water to the mixture at 60 ℃ and cool the solution to 25 ℃. Due to the formation of L/D-Lys@M-1 co-assembly, the transparent solution gradually becomes an opaque suspension. The photoluminescence spectra, UV absorption spectra and DLS (dynamic light scattering) were used to characterize the structure and photoluminescence properties of the photoluminescence components. It was found that L/D-Lys@M-1 had self-aggregation effect under the photoluminescence, its particle size increased from ca. 700 nm to ca. 1400 nm, and it produced continuously enhanced emission at 450 nm and 550 nm. The chiral properties of ground state and excited state were studied by CD (circular dichroism) and CPL. The Cotton effect was observed at 250 nm and 300 nm under solvent-induced and light-controlled conditions, and the CD intensity of the L/D-Lys@M-1 co-assembly system increased with prolonged illumination time, indicating that the co-assembly system realized chiral transfer and amplification. CPL spectra indicate that, under the solvent effect of poor solvent H2O, the co-assembly induced CPL signal at 540 nm (M-1 molecule fluorescence emission), luminescent dissymmetry factor (|glum|) 0.3×10-2. This study provides a strategy for CPL construction and dynamic regulation of achiral fluorescence molecules.
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