Stable Mono‐radical and Triplet Diradicals Based on Allylic Radical‐Embedded All‐benzenoid Polycyclic Hydrocarbons

Abstract High‐spin organic radicals are notable for their unique optical, electronic, and magnetic properties, but synthesizing stable high‐spin systems is challenging due to their inherent reactivity. This study presents a novel strategy for designing stable high‐spin polycyclic hydrocarbons (PHs) by incorporating allylic radical into fused aromatic benzenoid rings. To enhance stability, large steric hindrance groups with a synergistic captodative effect were added to the allylic radical centers. This approach was applied to synthesize derivatives of two open‐shell all‐benzenoid PHs: benzo[ fg ]tetracene ( 1 ) and dibenzo[ fg , lm ]heptacene ( 2 ). Both compounds exhibited excellent stability, with diradical 2 showing a half‐life of up to 17.2 days under ambient conditions. Bond length analysis and theoretical calculations suggest that 1 and 2 predominantly feature Clar's aromatic sextet structures with embedded allylic radicals. Compound 2 was confirmed to have a triplet ground state through DFT calculations and experimental methods, including pulse EPR spectroscopy and SQUID measurements. This work introduces a new design strategy for stable high‐spin hydrocarbons, paving the way for future developments in high‐spin organic materials.