Dinaphtho[1,2-b:2′,1′-d]chalcogenophenes: Comprehensive Investigation of the Effect of the Chalcogen Atoms in the Phenacene-Type π-Electronic Cores

We report dinaphtho[1,2- b:2′,1′- d ]chalcogenophenes as a new class of highly potential p-type semiconductors. As the result of comprehensive investigations including computational studies based on single-crystal structures successfully determined by X-ray analysis, the impacts of the chalcogen atoms are substantially manifested in their molecular orbitals, crystal packing structures, charge-transporting properties, and the device performances at the end. Among them, dinaphtho[1,2- b:2′,1′- d ]thiophene and dinaphtho[1,2- b:2′,1′- d ]selenophene achieved a hole mobility of up to 1.6 and 2.0 cm 2 V –1 s –1, respectively, accompanied by an I on / I off ratio as high as 10 4 –10 5 in their single-crystal organic field-effect transistors. Such high performances are attributed to the large orbital coefficient on the chalcogen atoms and the ideal packing structures induced by chalcogen-bridged W-shaped molecules.