1,2,5,6-Naphthalenediimide Based Donor–Acceptor Copolymers Designed from Isomer Chemistry for Organic Semiconducting Materials

Two new donor–acceptor (D–A) copolymers based on 1,2,5,6-naphthalenediimides (iso-NDI) and thiophene units, iso-P(NDI2OD-T2) and iso-P(NDI2OD-TT), were designed from isomer chemistry and compared with the reported isomeric copolymers P(NDI2OD-T2) and P(NDI2DT-TT) to investigate the influence of isomeric structure on their optoelectronic properties. DFT calculations reveal that iso-P(NDI2OD-T2) and iso-P(NDI2OD-TT) have higher HOMO and LUMO energies and better backbone planarity relative to their isomeric polymers. Iso-P(NDI2OD-T2) and iso-P(NDI2OD-TT) were synthesized by the Stille coupling polymerization and characterized by elemental analysis, 1 H NMR, GPC, UV–vis absorption, cyclic voltammetry, TGA, DSC, and organic thin film transistors (OTFTs). It was found that iso-P(NDI2OD-T2) and iso-P(NDI2OD-TT) had higher LUMO energies and broader band gaps than their isomeric ones and showed hole-dominated charge transport behavior, which is quite different from the electron-dominated charge transport feature of P(NDI2OD-T2) and P(NDI2DT-TT). In spite of the amorphous-like thin-film features, iso-P(NDI2OD-T2) exhibited high hole mobility of up to 0.3 cm 2 V –1 s –1, and iso-P(NDI2OD-TT) showed ambipolar property with hole and electron mobility of up to 0.02 and 4 × 10 –3 cm 2 V –1 s –1, respectively.