Illuminating Olympicenes: Insights Into Anti‐Kasha Photophysics in Polycyclic Aromatic Hydrocarbons

ABSTRACT Olympicene, or 6 H ‐benzo[ cd ]pyrene, is a polycyclic aromatic hydrocarbon (PAH) with five fused six‐membered rings arranged in a pattern reminiscent of the Olympic symbol. While functionalized olympicene‐based materials have captivated attention for their unique graphene‐fragment topology and aromaticity, their photoluminescent properties remain virtually unexplored. Here, we synthesize olympicene‐core functionalized derivatives and report their “anomalous” photophysical properties. These olympicene derivatives display extensive vibronic structure and highly interacting electronic states. Such effects give rise to excited‐state dynamics that are rare and unconventional in small PAH systems. Specifically, these olympicene derivatives exhibit dual fluorescence upon photoexcitation, accompanied by pronounced excitation‐dependent emission behavior. Spectroscopic evidence demonstrates these behaviors arise from multiple singlet emissive states—an anti‐Kasha locally excited (LE) state ( S n , n ≥ 2) and an intramolecular charge transfer (ICT) state. This work positions olympicene‐functionalized derivatives as a new platform to study fundamental photophysics. Exploring these properties will lead to new and advanced optoelectronic applications.