State Key Laboratory of Organic Electronics and Information Displays (KLOEID), Institute of Advanced Materials (IAM), Nanjing University of Posts & Telecommunications, 9 Wenyuan Road, Nanjing, 210023, China.
School of Chemistry and Chemical Engineering, Southeast University, No.2 SEU Road, Nanjing, 211189, China.
Chemistry. 2022 Nov 11;28(63):e202202336. doi: 10.1002/chem.202202336. Epub 2022 Sep 6.
Molecular motions are closely associated with the behaviors and properties of organic materials. However, monitoring molecular motions is challenging. Herein, a chiral supramolecular system consisting of L-/D-phenylalanine (LPF/DPF) as a chiral inducer and an achiral tetraphenylethene derivative (TPEF) as a molecular rotor has been proposed and explored for real-time discriminating the supramolecular motions by the visualization of circularly polarized luminescence (CPL) signal variations. Derived from the ordered molecular motions of TPEF induced by LPF/DPF, highly organized aggregates have been progressively assembled in a controlled manner with differentiated morphologies, including spherical particles, one-dimensional fibers, and floor-shaped supercrystals. Notably, increasing level of ordered aggregates, in turn, led to quenching emissions, while the CPL signals have been dramatically amplified accompanying by a sharp enhancement of luminescence dissymmetry factors (g ) from nearly 0 to -0.1. The significant amplification of CPL is attributed to the ordered aggregates of supramolecules, leading to the decrease of electric transition dipole moments in supramolecular system. As a result of the chiral supramolecular motions powered by supramolecular crystallization, the supramolecular motions are conveniently discriminated by visual CPL signal variation with an enhancement of g value from 0 to -0.1 in real time.
分子运动与有机材料的行为和性质密切相关。然而,监测分子运动具有挑战性。在此,我们提出并研究了一种由 L-/D-苯丙氨酸(LPF/DPF)作为手性诱导剂和非手性四苯乙烯衍生物(TPEF)作为分子转子组成的手性超分子体系,通过圆偏振发光(CPL)信号变化的可视化来实时区分超分子运动。源于 LPF/DPF 诱导的 TPEF 的有序分子运动,高度有序的聚集体以受控的方式逐步组装,具有不同的形态,包括球形颗粒、一维纤维和地板状超晶体。值得注意的是,有序聚集体的水平增加,依次导致发射猝灭,而 CPL 信号则显著放大,同时发光不对称因子(g )从近 0 急剧增强至-0.1。CPL 的显著放大归因于超分子的有序聚集,导致超分子体系中电跃迁偶极矩的减小。由于超分子结晶提供的手性超分子运动,超分子运动可以通过实时可视化 CPL 信号变化方便地区分,g 值从 0 增强至-0.1。