Dual‐Engineered DPP Polymers: Synergistic Hydrogen Bonding and Ring‐Fusion for High‐Mobility Organic Field‐Effect Transistors

Abstract Developing simple and effective molecular design strategies to optimize charge transport mobility remains a key challenge in high‐performance organic semiconductors. In this study, we integrate hydrogen bonding (H‐B) and ring‐fusion (R‐F) into a diketopyrrolopyrrole (DPP)‐based polymer, yielding a novel material, P‐HF. For comparison, a reference polymer (P‐B) and a hydrogen‐bonded analogue (P‐H) were synthesized. The synergistic effects of H‐B and R‐F dramatically not only enhance both inter‐ and intramolecular charge transport but also optimize the frontier orbital levels; H‐B strengthens intermolecular interactions, enabling localized ordered molecular packing and tighter π–π stacking, while R‐F further amplifies these effects meanwhile improving backbone planarity, extending π‐conjugation, and optimizing frontier orbital levels. As a result, P‐HF achieves an outstanding hole mobility of 5.02 cm 2 V −1 s −1 , surpassing P‐B (0.71 cm 2 V −1 s −1 ) and P‐H (2.13 cm 2 V −1 s −1 ), placing it among the highest‐performing DPP‐based polymers reported. This work demonstrates that combining R‐F and H‐B offers a viable strategy for designing high‐mobility conjugated materials, potentially advancing organic semiconductor development. This dual‐engineering strategy is particularly suitable for π‐conjugated polymers containing both hydrogen‐bonding sites and ring‐fused backbones.