LAUSR

Despite the great promise of armchair graphene nanoribbons (aGNRs) as high-performance semiconductors, practical band-gap engineering of aGNRs remains an unmet challenge. Given that width and edge structures are the two key factors for modulating band-gaps of aGNRs, a reliable synthetic method that allows control of both factors would be highly desirable. Here we report a simple modular strategy for efficient preparation of N = 6 aGNR, the narrowest member in the N = 3p (p: natural number) aGNR family, and two unsymmetrically edge-functionalized GNRs that contain benzothiadiazole and benzotriazole moieties. The trend of band-gap transitions among these GNRs parallels those in donor–acceptor alternating conjugated polymers. In addition, post-functionalization of the unsymmetrical heterocyclic edge via C–H borylation permits further band-gap tuning. Therefore, this method opens the door for convenient band-gap engineering of aGNRs through modifying the heteroarenes on the edge.Effective band-gap engineering of armchair graphene nanoribbons calls for control over both width and edge structure. Here, the authors report a modular synthesis of narrow N = 6 armchair graphene nanoribbons whose edges can be unsymmetrically modified with heteroarenes, introducing a simple way to tune band gap.