To date, supramolecular chemistry techniques have been applied to fullerene polymer synthesis, enabling the development of mainchain fullerene polymers whose primary structure is well regulated, including linear, dendritic, and net-like fullerene arrays. These research achievements have led to an intriguing scientific challenge to create main-chain fullerene polymers with higher structural regulation. Here, we report the fabrication of a helically organized fullerene array based on the supramolecular polymerization of chiral ditopic tetrakiscalix[5]arene hosts and a dumbbell-shaped fullerene. The molecular association between the chiral hosts and the dumbbell-shaped fullerene resulted in sizable supramolecular polymers in solution, with the highest degree of polymerization of more than 32. The achiral dumbbell-shaped fullerene exhibited circular dichroism in the π−π* transition bands arising from the fullerene moieties through supramolecular polymerization. End-capping experiments of the supramolecular helical polymers showed that the chirally twisted conformation of the dumbbell-shaped fullerene was directed by supramolecular polymerization. Finally, the helical morphology of the supramolecular polymer chain was visualized by atomic force microscopy. The successful development of helical main-chain fullerene polymers would break new ground in fullerene chemistry.

The dynamic helix interconversion of the C60-appended polyacetylene was directed by the molecular recognition of a chiral biscalix[5]arene.

We describe self-sorting supramolecular polymerization that uses chiral calix[5]arene hosts and a dumbbell-shaped fullerene guest. In a solution containing the racemic host and the guest, the (S)-host and the (R)-host...