Wang Yuxiang, Cui Liwen, Wang Yiran, Li Fei, Li Yunzhi, Meng Qi
Jiangsu Province Key Laboratory of Fine Petrochemical Engineering, School of Petrochemical Engineering, Changzhou University, No. 21, Gehu Rd., Wujin Dist., Changzhou, 213164, China.
School of Chemistry and Chemical Engineering, Linyi University, North Industrial Ave., Lanshan Dist., Linyi, 276000, China.
Chemistry. 2023 Dec 6;29(68):e202302373. doi: 10.1002/chem.202302373. Epub 2023 Oct 20.
Chiral macrocycles with circularly polarized luminescence (CPL) have attracted increasing attention due to the rigid structure, symmetrical chiral geometry and large luminescence dissymmetry factors (g ). However, most chiral macrocycles are more emissive in solutions but have weakened fluorescence quantum yields (Φ ) in aggregates, limiting their further application. In this paper, chiral macrocycle R/S-PhTPE was synthesized by combining chiral macrocycle architectonics with Z-o-phenyltetraphenylethylene (PhTPE) foldamer. Enhanced solution state emission and characteristic aggregation enhanced emission (AEE) effect can be observed for R/S-PhTPE due to the folded PhTPE conformation. Macrocycle immobilization and folded conformation endow PhTPE moiety with stable helical conformation. Most importantly, R/S-PhTPE exhibits opposite CPL signals compared with common chiral TPEs, demonstrating the evident impact of folded conformation. This work reports the first and deep insights into the chiroptical properties of chiral PhTPE foldamers, and will provide a new strategy to tune Φ and CPL signals of AIE active chiral macrocycles.
具有圆偏振发光（CPL）的手性大环化合物因其刚性结构、对称的手性几何形状和较大的发光不对称因子（g）而受到越来越多的关注。然而，大多数手性大环化合物在溶液中发射较强，但在聚集体中荧光量子产率（Φ）会减弱，这限制了它们的进一步应用。在本文中，通过将手性大环化合物构筑学与Z型邻苯基四苯乙烯（PhTPE）折叠体相结合，合成了手性大环化合物R/S-PhTPE。由于PhTPE的折叠构象，R/S-PhTPE在溶液态发射增强，并表现出特征性的聚集诱导发光（AEE）效应。大环固定化和折叠构象赋予PhTPE部分稳定的螺旋构象。最重要的是，与常见的手性TPE相比，R/S-PhTPE表现出相反的CPL信号，证明了折叠构象的明显影响。这项工作首次深入报道了手性PhTPE折叠体的手性光学性质，并将为调节聚集诱导发光（AIE）活性手性大环化合物的Φ和CPL信号提供一种新策略。
