© 2020 The Chemical Society of Japan. We have developed the synthesis of 1,3,6,8-tetramethoxy-2,7-diazapyrene through reductive aromatization of naphthalene diimide. The methoxy groups were readily converted to a variety of alkyl groups through Ni-catalyzed cross-coupling reaction with alkyl Grignard reagents. The peripheral substituents significantly influenced the packing structures of 2,7-diazapyrenes in the solid state.