Ambipolar Organic Field‐Effect Transistors from Cross‐Conjugated Aromatic Quaterthiophenes; Comparisons with Quinoidal Parent Materials

This contribution presents an electrochemical, Raman spectroscopic, and theoretical study probing the differences in molecular and electronic structure of two quinoidal oligothiophenes (3′,4′‐dibutyl‐5,5″‐bis(dicyanomethylene)‐5,5″‐dihydro‐2,2′:5′,2″‐terthiophene and 5,5′‐bis(dicyanomethylene)‐3‐hexyl‐2,5‐dihydro‐4,4′‐dihexyl‐2,2′,5,5′‐tetrahydro‐tetrathiophene) with terminal tetracyanomethylene functionalization and aromatic oligothiophenes where acceptor moieties are positioned at lateral positions along the conjugated chain (6,6′‐dibutylsulfanyl‐[2,2′‐bi‐[4‐dicyanovinylene‐4H‐cyclopenta[2,1‐b:3,4‐b′]dithiophene]). In this way, the consequences of linear and cross conjugation are compared and contrasted. From this analysis, it is apparent that organic field‐effect transistors fabricated with cross‐conjugated tetrathiophene semiconductors should combine the benefits of an electron‐donor aromatic chain with strongly electron‐accepting tetracyanomethylene substituents. The corresponding organic field‐effect transistors exhibit ambipolar transport with rather similar hole and electron mobilities. Moreover, n‐channel conduction is enhanced to yield one of the highest electron mobilities found to date for this type of material.