Functional Sulfur-Doped Buckybowls and Their Concave-Convex Supramolecular Assembly with Fullerenes

Buckybowls are fascinating components of supramolecular assemblies owing to their unique bowl‐shaped π‐surfaces. Herein we present a protocol for the functionalization of a sulfur‐doped buckybowl, trithiasumanene, via a brominated intermediate, from which thiolated trithiasumanenes were derived. The curved surface and electron‐donating properties of thiolated trithiasumanenes promote their ready assembly with fullerenes to form concave–convex complexes. The supramolecular assembly behavior in solution was investigated by NMR analysis. The structures of supramolecular complexes were unambiguously characterized by crystallography. The crystals of the concave–convex complexes showed high thermal stability and photoconductivity. Like a hand in a glove: When decorated with electron‐donating thiol groups, trithiasumanenes assembled with fullerenes both in solution and in the solid state. The supramolecular complexes were unambiguously characterized by X‐ray diffraction, which revealed their concave–convex supramolecular recognition (see picture). The crystals of the supramolecular complexes showed remarkable thermal stability and high photoconductivity.