-Extended Diaza[7]helicenes with Dual Negatively Curved Heptagons: Extensive Synthesis and Spontaneous Resolution into Strippable Homochiral Lamellae with Helical Symmetry

We report a unique category of pi-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 pi-extension on the carbazole moieties subsequently leads to a more sophisticated C2-symmetric homochiral triple helicene. Notably, these pi-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 mu m can be readily fabricated by flash aggregation. Distinctive pi-extended diaza[7]helicenes with fused negative curvature and helicity have been facilely synthesized by twofold heptagonal cyclization. In addition to intriguing features arising from the dynamic chiral skeleton, the molecular packing of these curved helicenes can be modulated by the periphery groups and the extension of the skeleton. This leads to the formation of crystals with 31 helices and also homochiral nanosheets upon exfoliation. image