螺旋烯
堆积
分子内力
结晶学
咔唑
化学
分子
外消旋化
手性(物理)
立体化学
光化学
对称性破坏
手征对称破缺
有机化学
Nambu–Jona Lasinio模型
物理
量子力学
作者
Fuwei Gan,Guoli Zhang,Juncong Liang,Chengshuo Shen,Huibin Qiu
标识
DOI:10.1002/ange.202320076
摘要
We report a unique category of π‐extended diaza[7]helicenes with double negative curvatures. This is achieved by two‐fold regioselective heptagonal cyclization of the oligoarylene‐carbazole precursors through either intramolecular C‐H arylation or Scholl reaction. The fusion of two heptagonal rings in the helical skeleton dramatically increases the intramolecular strain and forces the two terminal carbazole moieties to stack in a compressed fashion. The presence of the deformable negatively curved heptagonal rings endows the resulting diaza[7]helicenes with dynamic chiral skeletons, aggregation‐induced emission feature and relatively low racemization barrier of ca. 25.6 kcal·mol‐1. Further π‐extension on the carbazole moieties subsequently leads to a more sophisticated C2‐symmetric homochiral triple helicene. Notably, these π‐extended diaza[7]helicenes show structure‐dependent stacking upon crystallization, switching from heterochiral packing to intra‐layer homochiral stacking. Interestingly, the C2‐symmetric triple helicene molecules spontaneously resolve into a homochiral lamellar structure with 31 helix symmetry. Upon ultrasonication in a nonsolvent, the crystals can be readily exfoliated into large‐area ultrathin nanosheets with height of ca. 4.4 nm corresponding to two layers of stacked triple helicene molecules and relatively thicker nanosheets constituted by even‐numbered molecular lamellae. Moreover, regular hexagonal thin platelets with size larger than 30 μm can be readily fabricated by flash aggregation.
科研通智能强力驱动
Strongly Powered by AbleSci AI