Palladium-catalyzed pentannulation of polycyclic aromatic hydrocarbons

We present a new and versatile one-step synthesis of a series of small molecular chromophores based on cyclopentannulated polycyclic aromatic hydrocarbons (PAH). Easily available pyrene, anthracene, and perylene bromides serve as starting materials for the reactions. The formation of the five-membered ring is achieved by the straightforward palladium(0)-catalyzed carbannulation with various substituted acetylenes. This approach is applicable either to single or multiple annulation procedures leading to hitherto inaccessible PAH topologies. According to the resulting products of the diverse reactions, a mechanistic explanation is proposed. UV/Vis absorption as well as cyclovoltammetric measurements were performed for characterization demonstrating the value of this annulation technique. Optical absorptions of up to 780 nm and absorption coefficients ranging from 8000 to 34,000 M(-1) cm(-1) were detected.