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 cm2 V–1 s–1, respectively, accompanied by an Ion/Ioff ratio as high as 104–105 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.