Corannulene‐Driven Curvature Engineering Enhances Fullerene Encapsulation in a Carbon Nanohoop

Integrating intrinsically positively curved polycyclic aromatic hydrocarbons (PAHs) into cycloparaphenylene (CPP) frameworks remains challenging. In this study, we report a concise synthesis of a functionalized dibenzocorannulene unit via sulfone addition, followed by its seamless fusion into a CPP backbone to afford the positively curved nanohoop DBCora[10]CPP . This unique architecture creates a deep cavity with pronounced concave‐convex geometric complementarity toward fullerenes, resulting in strong binding affinities of up to 10 8 M −1 . 1 H NMR studies reveal slow host‐guest exchange behaviors in solution, while single‐crystal x‐ray diffraction unambiguously establishes the structure of C 60 @DBCora[10]CPP and reveals a distinctive octahedral packing motif featuring a free fullerene at the center. Femtosecond transient absorption spectroscopy demonstrates that the precise geometric match between host and guest enables ultrafast charge‐separation followed by a persistent charge‐separated (CS) state with a lifetime of 1.5 ns. Notably, this performance is achieved in a purely host‐guest assembly without the need for mechanical bonds or bulky stoppers. These findings demonstrate how positive‐curvature engineering can simultaneously modulate fullerene recognition, host‐guest dynamics, and charge‐separation behavior, establishing a useful design principle for functional carbon nanohoops and supramolecular optoelectronic systems.