Belt-Shaped <b>[20]Collarene</b> with a Rigid Yet Adaptable Cavity for Multimodal Fullerene Complexation

Collarenes, in which alternating benzenoid and 1,4-cyclohexadiene rings are fused to form belt-shaped hydrocarbons, show exceptional promise as molecular containers in supramolecular chemistry. However, the experimental investigation of their host–guest chemistry remains largely untapped. Herein, we report multimodal complexation behaviors between [20]collarene and a series of fullerenes. [20]Collarene is capable of complexing both C 60 and C 70 to form inclusion complexes, as confirmed by proton nuclear magnetic resonance spectroscopy, isothermal titration calorimetry, high-resolution mass spectrometry, and single-crystal X-ray crystallography. The strong binding affinities for fullerenes ( K a up to 10 5 M –1 ) lead to host–guest complexes that display ultrafast charge separation and a stable charge-separated state. Moreover, [20]collarene possesses a shape-adaptable cavity when complexing with two fullerene derivatives, PC61BM and DPC61Py, via different complexation modes. Specifically, [20]collarene exhibits fully encapsulated host–guest complexation with PC61BM, whereas it engages in solvent-synergistic complexation with DPC61Py . This work systematically establishes the host–guest chemistry of [20]collarene with a rigid yet adaptive cavity, thereby laying a crucial foundation in the field of collarene-based supramolecular chemistry and guiding its future development toward functional materials.