Thiazole Imide-Based All-Acceptor Homopolymer: Achieving High-Performance Unipolar Electron Transport in Organic...

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 (μ_e ) of 1.61 cm² V^-1 s^-1 , low off-currents (I_off ) of 10^-10 -10^-11 A, and substantial current on/off ratios (I_on /I_off ) 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 I_off s > 10^-8 A and small I_on /I_off 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.