Radical C─N Coupling at Electrified Carbon Nanotube Interfaces

ABSTRACT Nitrogen‐containing motifs are central to pharmaceuticals, materials, and bioactive molecules, yet controlling radical C─N bond formation under mild and catalyst‐free conditions remains challenging. Here, we report an electrified carbon nanotube (CNT) interface that promotes radical C─N coupling of aniline derivatives and N ‐containing heterocyclic compounds under ambient conditions. Mechanistic experiments show that the enhanced reactivity arises from the coupling of the applied electric field with interfacial charge transfer through the CNT network. Radical trapping, redox probing, and density functional theory calculations support a field‐assisted electron‐transfer pathway involving nitrogen‐centered radical intermediates. Our results indicate that the applied field lowers the barrier to radical generation, underscoring its critical role in enabling the reaction. This work demonstrates that conductive nanointerfaces can enable localized radical bond‐forming chemistry under an externally applied electric field.