Radically Accessing D–A Type Ambipolar Copolymeric Materials with Intrinsic Electrical Conductivity and Visible–Near Infrared Absorption Via Electro‐Copolymerization

Thienothiadiazole‐bisthiophene (TTDT₂) and diketopyrrolo–pyrrole–bisthiophene (DPPT₂) are successfully electro‐copolymerized with terthiophene (T₃) as an initiator and linker at low oxidative potentials. AC impedance analysis, absorption spectroscopy, and elemental composition via SEM‐EDX support the formation of donor–acceptor (D–A) type alternating block copolymers, poly(T₃‐TTDT₂), and poly(T₃‐DPPT₂). Unique optical properties that span into the near infrared‐II(>1000 nm) region and inherent electrical conductivity at the p‐type regime, n‐type regime, and in between the two regimes (i.e., typical insulator region) are observed. This study showcases the advantages of electro‐polymerization toward tailoring of next generation opto‐electronic materials.