Small band gap molecular semiconductors are of interest for the development of transparent electronics. Here we report two near-infrared (NIR), n-type small molecule semiconductors, based upon an acceptor–donor–acceptor (A-D-A) approach. We show that the inclusion of molecular spacers between the strong-electron-accepting end group, 2,1,3-benzothiadiazole-4,5,6-tricarbonitrile, and the donor core affords semiconductors with very low band gaps down to 1 eV. Both materials were synthesized by a one-pot, 6-fold nucleophilic displacement of a fluorinated precursor by cyanide. Significant differences in solid-state ordering and charge carrier mobility are observed depending on the nature of the spacer, with a thiophene spacer resulting in solution processed organic field-effect transistors (OFETs) exhibiting excellent electron mobility up to 1.1 cm2 V–1 s–1. The use of silver nanowires as the gate electrode enables the fabrication of a semitransparent OFET device with an average visible transmission of 71% in the optical spectrum.