Precise Donor‐Acceptor Engineering for High‐Mobility Ambipolar Emissive Polymer Semiconductors

Comprehensive Summary Conjugated polymers are promising platforms for integrated optoelectronics, yet in most reported high mobility diketopyrrolopyrrole (DPP)‐based semiconductors, strong intermolecular aggregation and narrow bandgaps suppress luminescence, limiting their applicability in multifunctional devices. The concurrent realization of efficient charge transport and strong thin film emission therefore remains a fundamental challenge. Here, we report two novel DPP‐derived polymers, PTFBVDPP‐V and PTFBVDPP‐TVT, synthesized via Stille coupling through precise donor‐acceptor (D‐A) engineering. Both polymers possess highly coplanar backbones, forming continuous fiber networks and ordered crystalline films with close intermolecular π‐π stacking. Polymer PTFBVDPP‐V functions as a unipolar n‐type semiconductor with an electron mobility ( μ e ) of 2.61 cm 2 ·V −1 ·s −1 but negligible emission. In contrast, precise D–A modulation in PTFBVDPP‐TVT enables balanced ambipolar transport with a hole mobility of 1.52 cm 2 ·V −1 ·s −1 and an electron mobility of 1.15 cm 2 ·V −1 ·s −1 , while retaining a thin‐film photoluminescence quantum yield ( Φ ) of 6.5%. This combination delivers a maximum Φ · μ e exceeding 10 −2 cm 2 ·V −1 ·s −1 , establishing a record performance among high‐mobility ambipolar emissive polymer semiconductors and breaking the long‐standing trade‐off between charge transport and luminescence in conventional high‐mobility DPP‐based systems.