Solution‐Processable and Ambient‐Stable Highly Conductive p‐Type Polymers Derived from Dihydropyrazine and Ethylenedioxythiophene

Abstract π‐Conjugated polymers (CPs) with high conductivity, solution processability, and ambient stability are vital for advancing printed electronics. However, achieving conductivities over 1000 S cm⁻¹ remains challenging. This study introduces a series of solution‐processable p‐type donor–acceptor (D‐A) CPs based on dihydropyrazine (DHP) and ethylenedioxythiophene (EDOT) that address this limitation. The design leverages the ability of DHP and EDOT to form open‐shell electronic configurations, which promote extended conjugation and efficient intrachain charge transport. Strong interchain donor‐acceptor interactions reduce π–π stacking distances, facilitating efficient interchain charge transport, while the electron‐rich EDOT units enhance p‐doping efficiency and stabilize the doped polymer. Additionally, the conformational locking effect of EDOT supports a face‐on chain orientation, facilitating charge transport, while spaced‐out alkyl side chains on DHP improve dopant diffusion. The polymers demonstrate exceptional conductivity, stability, scalability, and processability in eco‐friendly solvents, achieving conductivity values up to 1700 S cm⁻¹ through sequential doping with ferric chloride and Magic Blue under ambient conditions. This remarkable performance, attributed to a compact π–π stacking distance of 3.38 Å, face‐on chain orientation, and efficient doping, establishes the quinoidal DHP as a promising building block for the development of ultrahigh‐conductivity p‐type CPs, enabling advancements in printed electronics and flexible device applications.