Highly Efficient Mixed Conduction in a Fused Oligomer n‐Type Organic Semiconductor Enabled by 3D Transport Pathways

Abstract Tailoring organic semiconductors to facilitate mixed conduction of ionic and electronic charges when interfaced with an aqueous media has spurred many recent advances in organic bioelectronics. The field is still restricted, however, by very few n‐type (electron‐transporting) organic semiconductors with adequate performance metrics. Here, a new electron‐deficient, fused polycyclic aromatic system, TNR, is reported with excellent n‐type mixed conduction properties including a µC* figure‐of‐merit value exceeding 30 F cm⁻¹ V⁻¹ s⁻¹ for the best performing derivative. Comprising three naphthalene bis‐isatin moieties, this new molecular design builds on successful small‐molecule mixed conductors; by extending the molecular scaffold into the oligomer domain, good film‐forming properties, strong π–π interactions, and consequently excellent charge‐transport properties are obtained. Through judicious optimization of the side chains, the linear oligoether and branched alkyl chain derivative bgTNR is obtained which shows superior mixed conduction in an organic electrochemical transistor configuration including an electron mobility around 0.3 cm² V⁻¹ s⁻¹. By optimizing the side chains, the dominant molecular packing can be changed from a preferential edge‐on orientation (with high charge‐transport anisotropy) to an oblique orientation that can support 3D transport pathways which in turn ensure highly efficient mixed conduction properties across the bulk semiconductor film.