We show that polycyclic aromatic hydrocarbon (PAH) chromophores that are linked between two fivemembered rings can access planarized structures with reduced optical gaps and redox potentials. Two aceanthrylene chromophores were connected into dimer model systems with the chromophores either projected outward (2,2′biaceanthrylene) or inward (1,1′-biaceanthrylene), and the optical and electronic properties were compared. Only the planar 2,2′-biaceanthrylene system showed significant reductions of the optical gaps (1 eV) and redox potentials in relation to the aceanthrylene monomer. Organic field effect transistors based on 2,2′-biaceanthrylene were prepared and were found to operate in the hole transport regime with an average charge carrier mobilities of 1.8 × 10 −4 cm 2 V −1 s −1 .