Highly Selective Construction of D ₂ ‐Symmetric Chiral Carbon Nanorings and the Diverse Assembly With Fullerenes

Chiral carbon nanorings have attracted significant attention due to their unique structures and properties. However, their synthesis faces challenges such as low selectivity and tedious separation processes, while their hierarchical supramolecular self‐assembly behaviors remain largely unexplored. In this study, we designed a chiral fused‐ring building block with a nearly right‐angle bend, enabling the efficient construction of chiral carbon nanorings with D 2 symmetry, namely D 2 ‐(P)‐NR3 and D 2 ‐(M)‐NR3 . The resulting nanorings exhibited diverse multi‐level cooperative assembly with fullerene molecules. At the host–guest level, C 60 was encapsulated within the nanoring cavity in an “in‐ring” binding mode. In contrast, the larger C 70 was accommodated above the cavity in an “on‐ring” fashion, forming a host–guest complex reminiscent of a “straw hat.” At a higher level of assembly, the C 60 ‐based complexes further self‐organized into a 4‐fold superhelix, while the “straw hat”‐shaped complexes of C 70 stacked via concave–convex complementarity to form one‐dimensional tubular structures. On the mesoscopic scale, the C 60 complexes assembled into helical nanofibers, whereas the C 70 complexes formed microplates.