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We report the first example of a donor–acceptor corannulene‐containing hybrid material with rapid ligand‐to‐ligand energy transfer (ET). Additionally, we provide the first time‐resolved photoluminescence (PL) data for any corannulene‐based compounds in the solid state. Comprehensive analysis of PL data in combination with theoretical calculations of donor–acceptor exciton coupling was employed to estimate ET rate and efficiency in the prepared material. The ligand‐to‐ligand ET rate calculated using two models is comparable with that observed in fullerene‐containing materials, which are generally considered for molecular electronics development. Thus, the presented studies not only demonstrate the possibility of merging the intrinsic properties of π‐bowls, specifically corannulene derivatives, with the versatility of crystalline hybrid scaffolds, but could also foreshadow the engineering of a novel class of hierarchical corannulene‐based hybrid materials for optoelectronic devices.

Hierarchical Corannulene‐Based Materials: Energy Transfer and Solid‐State Photophysics