Electronic Control of Scholl Cyclization Trajectories Enables Direct Access to Trihetero-Quasi[8]circulenes

Quasi[8]circulenes remain challenging to access directly from polyaryl precursors because competing Scholl-type cyclization pathways obscure control over the annulation sequence. Here, we demonstrate that (hetero)aryl electronic programming directs oxidative cyclodehydrogenation to selectively generate S–, O–, and N-embedded quasi[8]circulenes from tailored tetrarylthiophenes. The resulting twisted π-architecture possesses induced paratropic COT cores, tunable optoelectronic properties, and persistent π-delocalized radical cations with near-infrared (NIR) absorption. Beyond hetero-quasi[8]circulenes, this work establishes electronic programming as a design principle for controlling complexity in oxidative π-framework construction.