Three new members of N-heteropentacenes explored herein have adjacent pyrazine and dihydropyrazine rings at one end of the pentacene backbone. Interesting findings from this study include self-complementary N-H···N H-bonds in the solid state, solvent-dependent UV-vis absorption caused by H-bonding, and new p-type organic semiconductors with field effect mobility up to 0.7 cm(2) V(-1) s(-1).