Thiazole Imide‐Based All‐Acceptor Homopolymer: Achieving High‐Performance Unipolar Electron Transport in Organic Thin‐Film Transistors

High-performance unipolar n-type polymer semiconductors are critical for advancing the field of organic electronics, which relies on the design and synthesis of new electron-deficient building blocks with good solubilizing capability, favorable geometry, and optimized electrical properties. Herein, two novel imide-functionalized thiazoles, 5,5'-bithiazole-4,4'-dicarboxyimide (BTzI) and 2,2'-bithiazolothienyl-4,4',10,10'-tetracarboxydiimide (DTzTI), are successfully synthesized. Single crystal analysis and physicochemical study reveal that DTzTI is an excellent building block for constructing all-acceptor homopolymers, and the resulting polymer poly(2,2'-bithiazolothienyl-4,4',10,10'-tetracarboxydiimide) (PDTzTI) exhibits unipolar n-type transport with a remarkable electron mobility (μe ) of 1.61 cm² V⁻¹ s⁻¹ , low off-currents (Ioff ) of 10⁻¹⁰ -10⁻¹¹ A, and substantial current on/off ratios (Ion /Ioff ) of 10⁷ -10⁸ in organic thin-film transistors. The all-acceptor homopolymer shows distinctive advantages over prevailing n-type donor-acceptor copolymers, which suffer from ambipolar transport with high Ioff s > 10⁻⁸ A and small Ion /Ioff s < 10⁵ . The results demonstrate that the all-acceptor approach is superior to the donor-acceptor one, which results in unipolar electron transport with more ideal transistor performance characteristics.