Zhou Qifeng, Yuan Wei, Li Yunfei, Han Yi, Bao Lintao, Fan Wei, Jiao Liuying, Zhao Yanli, Ni Yong, Zou Ya, Yang Hai-Bo, Wu Jishan
Department of Chemistry, National University of Singapore 3 Science Drive 3, Singapore, 117543, Singapore.
Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai, 200062, P. R. China.
Angew Chem Int Ed Engl. 2025 Jan 27;64(5):e202417749. doi: 10.1002/anie.202417749. Epub 2024 Nov 13.
π-Conjugated chiral shape-persistent molecular nanocarbons hold great potential as chiroptical materials, though their synthesis remains a considerable challenge. Here, we present a simple approach using Suzuki coupling of a [5]helicene building block with various aromatic units, enabling the one-pot synthesis of a series of chiral macrocycles with persistent figure-eight and Möbius shapes. Single-crystal structures of 7 compounds were solved, and 22 enantiomers were separated by preparative chiral HPLC. A notable pyrene-bridged figure-eight macrocycle, with its rigid, fully π-conjugated and overcrowded structure, exhibited pure excimer emission and outstanding circularly polarized luminescence (CPL) properties, including a large dissymmetric factor (|g|=3.8×10) and significant CPL brightness (B=710.5 Mcm). This method provides a versatile synthetic platform for producing various chiral D-symmetric figure-eight macrocycles and singly or triply twisted Möbius macrocycles with C and D symmetry, offering tunable chiroptical properties for CPL applications.
π-共轭手性形状持久分子纳米碳作为手性光学材料具有巨大潜力，尽管其合成仍然是一个相当大的挑战。在此，我们提出一种简单方法，利用[5]螺旋烯构建块与各种芳香单元的铃木偶联反应，实现一锅法合成一系列具有持久8字形和莫比乌斯形状的手性大环化合物。解析了7种化合物的单晶结构，并通过制备型手性高效液相色谱法分离出22种对映体。一种引人注目的芘桥连8字形大环化合物，具有刚性、完全π共轭且拥挤的结构，表现出纯激基复合物发射和出色的圆偏振发光（CPL）特性，包括大的不对称因子（|g| = 3.8×10）和显著的CPL亮度（B = 710.5 Mcm）。该方法为制备各种具有C和D对称性的手性D对称8字形大环化合物以及单重或三重扭曲的莫比乌斯大环化合物提供了一个通用的合成平台，为CPL应用提供了可调节的手性光学特性。
