Li Gaolei, Mao Liang-Liang, Gao Jia-Nan, Shi Xueliang, Huo Zi-Ye, Yang Jingxuan, Zhou Wen, Li Hongwei, Yang Hai-Bo, Tung Chen-Ho, Wu Li-Zhu, Cong Huan
Key Laboratory of Photochemical Conversion and Optoelectronic Materials, CAS-HKU Joint Laboratory on New Materials, Technical Institute of Physics and Chemistry, School of Future Technology, University of Chinese Academy of Sciences, Chinese Academy of Sciences, Beijing, 100190, China.
Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai, 200062, China.
Angew Chem Int Ed Engl. 2025 Feb 10;64(7):e202419435. doi: 10.1002/anie.202419435. Epub 2024 Dec 4.
The bottom-up synthesis of discrete tubular molecules that mimic the structural features of carbon nanotubes has been a long-standing pursuit for synthetic chemists. As the shortest segments of armchair-type carbon nanotubes, cycloparaphenylenes are regarded as ideal macrocyclic building blocks for achieving this goal. Here we report the synthesis of a helical tubular molecule featuring three diyne linkers between two site-specifically functionalized [9]cycloparaphenylenes. Its C-symmetrical, radially conjugated structure and solid-state packing have been elucidated by spectroscopic and crystallographic characterizations. Notably, the resolved enantiomers display a circularly polarized luminescence brightness value of 1.47×10 M cm, which is among the highest values for chiral organic molecules. Furthermore, the diyne-linked molecule could be directly converted into a thiophene-linked helical molecule, demonstrating the post-functionalization approach for the construction of chiral tubular molecules from cycloparaphenylenes.
模拟碳纳米管结构特征的离散管状分子的自下而上合成一直是合成化学家长期追求的目标。作为扶手椅型碳纳米管的最短片段，环对亚苯基被视为实现这一目标的理想大环构建块。在此，我们报告了一种螺旋管状分子的合成，该分子在两个位点特异性功能化的[9]环对亚苯基之间具有三个二炔连接基。其C对称、径向共轭结构和固态堆积已通过光谱和晶体学表征得以阐明。值得注意的是，拆分得到的对映体显示出1.47×10 M cm的圆偏振发光亮度值，这是手性有机分子中的最高值之一。此外，二炔连接的分子可以直接转化为噻吩连接的螺旋分子，这展示了从环对亚苯基构建手性管状分子的后功能化方法。
