Delicate Regulation of Central Substituents Boosts Organic Photovoltaic Performance of Dimeric Acceptors

Dimeric acceptors are expected to satisfy both excellent power conversion efficiency (PCE) and operational stability of organic solar cells (OSCs). However, comparing to highly planar and symmetrical monomer‐like acceptors, the quite different steric/spatial configurations of dimeric acceptors affect device outcomes greatly. Herein, on basis of the same dimeric molecular platform that constructed by bridging central units of two monomer‐like acceptor, diverse substituents (─OCH 3 for D1, ─CH 3 for D2, and ─CF 3 for D3) are grafted on central units to regulate the three dimensions (3D) geometries of dimeric acceptors delicately. A systematic investigation reveals the substituent‐dependent variation of energy level, absorption, and molecular packing behavior. Consequently, D2 acceptor, characteristic of more favorable configuration, affords a superior film morphology and charge transfer/transport dynamics in resulting OSCs, thus yielding an excellent PCE of 17.50% along with a good long‐term stability. This work manifests the crucially important role of central substituents in constructing high‐performance dimeric acceptors.