Cyano-Functionalized Bithiophene Imide-Based n-Type Polymer Semiconductors: Synthesis, Structure–Property Correlations, and Thermoelectric Performance

n-Type polymers with deep-positioned lowest unoccupied molecular orbital (LUMO) energy levels are essential for enabling n-type organic thin-film transistors (OTFTs) with high stability and n-type organic thermoelectrics (OTEs) with high doping efficiency and promising thermoelectric performance. Bithiophene imide (BTI) and its derivatives have been demonstrated as promising acceptor units for constructing high-performance n-type polymers. However, the electron-rich thiophene moiety in BTI leads to elevated LUMOs for the resultant polymers and hence limits their n-type performance and intrinsic stability. Herein, we addressed this issue by introducing strong electron-withdrawing cyano functionality on BTI and its derivatives. We have successfully overcome the synthetic challenges and developed a series of novel acceptor building blocks, CNI, CNTI, and CNDTI, which show substantially higher electron deficiencies than does BTI. On the basis of these novel building blocks, acceptor–acceptor type homopolymers and copolymers were successfully synthesized and featured greatly suppressed LUMOs (−3.64 to −4.11 eV) versus that (−3.48 eV) of the control polymer PBTI. Their deep-positioned LUMOs resulted in improved stability in OTFTs and more efficient n-doping in OTEs for the corresponding polymers with a highest electrical conductivity of 23.3 S cm–1 and a power factor of ∼10 μW m–1 K–2. The conductivity and power factor are among the highest values reported for solution-processed molecularly n-doped polymers. The new CNI, CNTI, and CNDTI offer a remarkable platform for constructing n-type polymers, and this study demonstrates that cyano-functionalization of BTI is a very effective strategy for developing polymers with deep-lying LUMOs for high-performance n-type organic electronic devices.