Strong Proquinoidal Acceptor Enables High‐Performance Ambipolar Organic Electrochemical Transistors

Abstract Ambipolar organic electrochemical transistors (OECTs) can simplify manufacturing processes and reduce device footprints, yet their performance still lags behind their p‐type and n‐type counterparts due to limited molecular design strategies. Here, incorporating strong proquinoidal building blocks effectively addresses this challenge is demonstrated. Using a computational acceptor screening approach, three TBDOPV‐based polymers are designed and synthesized: P(bgTBDOPV‐T), P(bgTBDOPV‐EDOT), and P(bgTBDOPV‐MeOT2), all exhibiting ambipolar behavior across various donor moieties. Remarkably, P(bgTBDOPV‐EDOT) achieves record‐high figure‐of‐merit ( µC *) values, reaching 268 F cm −1 V −1 s −1 for p‐type and 107 F cm −1 V −1 s −1 for n‐type operations. Additionally, P(bgTBDOPV‐EDOT) exhibits low operation voltages ( V Th,p = −0.55 V and V Th,n = 0.32 V), with fast response times ( τ on / τ off = 0.48/0.36 ms for p‐type and 0.41/0.41 ms for n‐type) and enhanced operational stability. Inverter devices based on P(bgTBDOPV‐EDOT) show high voltage gains of 173 V/V. Theoretical calculations and data analysis confirm that strong proquinoidal acceptors significantly enhance the delocalization of both positive and negative polarons, offering an effective pathway for higher‐performance ambipolar OECT materials.