Highly Planarized Naphthalene Diimide–Bifuran Copolymers with Unexpected Charge Transport Performance

[Image: see text] The synthesis, characterization, and charge transport performance of novel copolymers PNDIFu2 made from alternating naphthalene diimide (NDI) and bifuran (Fu2) units are reported. Usage of potentially biomass-derived Fu2 as alternating repeat unit enables flattened polymer backbones due to reduced steric interactions between the imide oxygens and Fu2 units, as seen by density functional theory (DFT) calculations and UV–vis spectroscopy. Aggregation of PNDIFu2 in solution is enhanced if compared to the analogous NDI–bithiophene (T2) copolymers PNDIT2, occurring in all solvents and temperatures probed. PNDIFu2 features a smaller π–π stacking distance of 0.35 nm compared to 0.39 nm seen for PNDIT2. Alignment of aggregates in films is achieved by using off-center spin coating, whereby PNDIFu2 exhibits a stronger dichroic ratio and transport anisotropy in field-effect transistors (FET) compared to PNDIT2, with an overall good electron mobility of 0.21 cm(2)/(V s). Despite an enhanced backbone planarity, the smaller π–π stacking and the enhanced charge transport anisotropy, the electron mobility of PNDIFu2 is about three times lower compared to PNDIT2. Density functional theory calculations suggest that charge transport in PNDIFu2 is limited by enhanced polaron localization compared to PNDIT2.