Wang Sipeng, Wu Shengfu, Wang Runjia, Lu Jie, Liu Minghua
Beijing National Laboratory of Molecular Sciences and CAS Key Laboratory of Colloid, Interface and Thermodynamics, Institute of Chemistry, Chinese Academy of Sciences, North First Street 2, Zhongguancun, Beijing, 100190, China.
University of Chinese Academy of Sciences, No.19(A) Yuquan Road, Beijing, 100049, China.
Angew Chem Int Ed Engl. 2025 Aug 11;64(33):e202507992. doi: 10.1002/anie.202507992. Epub 2025 Jun 25.
The design and assembly of chiral macrocycles remain an underexplored frontier in supramolecular science. In this study, we synthesized a pair of enantiomeric macrocyclic molecules (CP1) through the condensation of chiral cyclohexanediamine with tetraphenylethylene (TPE) dialdehyde. These molecules exhibited remarkable circular dichroism (CD) and circularly polarized luminescence (CPL) properties at the supramolecular level. Through supramolecular assembly in mixed solvent systems, we achieved a rare micron-scale helical structure, exhibiting a high luminescence dissymmetry factor (g) of 0.32-one of the highest values reported to date for macrocyclic self-assemblies. Furthermore, by designing a chiral macrocycle with phenyl spacers (CP2), we revealed that the confinement of macrocycles and restricted internal molecular rotation are critical for achieving high g values and helical structure formation. This work not only advances the design of chiral macrocycles but also provides new insights into the relationship between molecular structure and supramolecular assembly, paving the way for the development of advanced chiral materials with potential applications in optics, sensing, and nanotechnology.
手性大环化合物的设计与组装仍是超分子科学中一个尚未充分探索的前沿领域。在本研究中，我们通过手性环己二胺与四苯乙烯（TPE）二醛缩合，合成了一对对映体大环分子（CP1）。这些分子在超分子水平上表现出显著的圆二色性（CD）和圆偏振发光（CPL）特性。通过在混合溶剂体系中的超分子组装，我们获得了一种罕见的微米级螺旋结构，其发光不对称因子（g）高达0.32，这是迄今为止大环自组装报道的最高值之一。此外，通过设计带有苯基间隔基的手性大环（CP2），我们发现大环的限制作用和受限的分子内旋转对于实现高g值和形成螺旋结构至关重要。这项工作不仅推动了手性大环化合物的设计，还为分子结构与超分子组装之间的关系提供了新的见解，为开发在光学、传感和纳米技术等领域具有潜在应用的先进手性材料铺平了道路。
