Supporting InformationGeneral. Melting points were obtained on a Yanaco melting point apparatus and uncorrected. EI mass spectra were collected on a SHIMADZU GCMS-QP5000 mass spectrometer. UV-vis spectra were recorded on a SHIMADZU Multi Spec-150.Emission spectra were collected on a SHIMADZU RF-1500 spectrometer. The calorimetric data were obtained on a Seiko Exter-5000 at a scanning rate 10 °C min -1 .Differential pulse voltammogram was recorded on a BAS-100B system containing terabutylammoniumhexafluorophoshate ( TBAPF 6 ) ( 0.1moldm -3 in dry THF ). The Pt disk, Pt wire and SCE were used as the working, counter, and reference electrodes, respectively.

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[structure: see text] A series of the title dicyanopyrazinoquinoxaline derivatives have been prepared and characterized by using single-crystal X-ray structure analysis and redox potential measurements. They have strong electron-accepting properties due to the pyrazinopyrazine skeletons as well as the cyano groups. Substituents can be easily introduced at the benzene ring and control the HOMO-LUMO energy gap and the molecular packing. They show clear n-type transistor properties in the FET devices.