Linker‐Mediated Delocalized Excited States in Dimeric Acceptors Enable Efficient Exciton Dissociation with Negligible Energy‐Level Offsets

Abstract Efficient exciton dissociation at low energy offsets is key to overcoming voltage losses in organic solar cells. In this work, we developed two dimeric acceptors, i‐YT and o‐YT, by precisely controlling the position of an asymmetric electron‐donating linker. It induced the foldamer conformation of i‐YT with a para linkage (relative to the dicyano groups), while retaining the unfold conformation for o‐YT. This subtle structural modification influenced the molecular assembly properties, enabled near‐zero energy offset exciton dissociation and power conversion efficiencies exceeding 18 % for i‐YT based organic solar cells. Detailed excitonic dynamics further revealed that the linker position critically influences three processes: the formation of delocalized singlet excited states, ultrafast charge transfer (~5 ps) in solid blends, and the suppression of exciton recombination. Additionally, devices based on i‐YT demonstrated outstanding long‐term stability, retaining 85 % of their initial efficiency after 1,400 hours of continuous illumination. These findings introduce a new class of dimeric acceptors that combine high efficiency with exceptional stability, offering a promising pathway toward low‐energy‐loss organic photovoltaics.