Conjugated polymers with a donor–acceptor (DA) structural motif have found extensive use in a wide variety of optoelectronic devices; however, despite their ubiquity in the literature, the vast majority of these materials are simple alternating copolymersone electron donor alternates with one electron acceptor in the polymer backbone. As a result, the impact of composition (e.g., donor/acceptor ratio) and structure (e.g., alternating, block, or random) on the optoelectronic properties of these copolymers remains poorly understood. In this work, the number of acceptor units in alternating DA copolymers is systematically increased. Two dimers of the common electron acceptor isoindigo are synthesized, one with free rotation between the subunits and one with enforced coplanarity. The two dimers are then used to synthesize donor–acceptor–acceptor (DAA) copolymers with either thiophene or terthiophene comonomers. These DAA polymers feature two electron acceptors in their repeat unit, and their optoelectronic properties are compared to those of the analogous DA polymers. It is shown that increasing the number of acceptor units causes a decrease in the LUMO energy of the resulting polymer; this effect is enhanced by enforcing coplanarity between acceptor units via ring fusion. All six polymers were tested in both organic photovoltaics (OPVs) and organic thin film transistors (OTFTs). While the DA polymers performed better in OPVs, the DAA polymers displayed more balanced charge carrier mobilities in OTFTs.

A novel small bandgap donor–acceptor polymer with a very small band gap of 0.95 eV shows promising photoresponse under near infrared light in phototransistors.