Aldol condensation-enabled acceptor-acceptor type bithiophene imide polymer semiconductors for n-type field-effect transistors

While the development of high-performing n-type polymer semiconductors remains a challenge, the involving of costly transition-metal catalysts and even toxic reagents during the preparation of these materials might also cause serious environmental issues. Herein, by devising two new aldehyde-functionalized bithiophene imide (BTI)-type building blocks, we designed and synthesized two acceptor-acceptor type n-type polymers, BTI-BD and BTI2-BD, on the basis of an environmentally benign, transition metal-free and thus cost-effective aldol condensation. The resulting polymers exhibited planar and rigid backbone conformations and low-lying LUMO energy levels close to −4.0 eV, thus leading to unipolar n-type tranport character with a highest electron mobility of 1.35 × 10⁻³ cm² V⁻¹ s⁻¹ in organic field-effect transistors for the BTI2-BD polymer which features a higher molecular ordering in solid state. Our results demonstrate that the aldol polycondensation strategy could serve as a cheaper and more ecofriendly alternative to the convential transition metal-catalyzed cross-coupling reactions for constructing n-type acceptor-acceptor polymers with unipolar n-type charge transport characteristics.