n‐Type Azaacenes Containing B←N Units

We disclose a novel strategy to design n-type acenes through the introduction of boron-nitrogen coordination bonds (B←N). We synthesized two azaacenes composed of two B←N units and six/eight linearly annelated rings. The B←N unit significantly perturbed the electronic structures of the azaacenes: Unique LUMOs delocalized over the entire acene skeletons and decreased aromaticity of the B←N-adjacent rings. Most importantly, these B←N-containing azaacenes exhibited low-lying LUMO energy levels and high electron affinities, thus leading to n-type character. The solution-processed organic field-effect transistor based on one such azaacene exhibited unipolar n-type characteristics with an electron mobility of 0.21 cm2  V-1  s-1 .