π‐Extension Assisted Macrocycle‐Encapsulated Non‐Fused Ring Electron Acceptors with Dual Charge Transporting Pathways for High‐Performance Organic Solar Cells

Abstract Achieving compact and ordered charge transfer channels is essential for high‐performance non‐fused ring electron acceptors (NFREAs). Herein, this is demonstrated that how the stacking arrangement of non‐fused ring molecules with macrocycle encapsulated can be regulated via π‐extension, thus resulting in nearly planar molecular backbones, more compact and ordered electron transfer channels with dual transport characteristics. In RTT‐TT‐4F , these pronounced aggregation features endow its blend film with appropriate phase separation, thereby reducing charge recombination, balancing charge carrier mobilities, and significantly lowering energy loss in OSCs. Consequently, RTT‐TT‐4F ‐based OSCs achieve remarkable power conversion efficiencies of 14.45% and 19.76% in binary and ternary devices, respectively. Our findings provide essential insights into the development of high‐performance NFREAs for OSC applications.