Design and Synthesis of N‐Alkylaniline‐Substituted Low Band‐Gap Electron Acceptors for Photovoltaic Application

Comprehensive Summary A novel electron donating unit, namely N ‐octyl‐ N ‐phenyl‐thiophene (OPT), was designed in preparing electron acceptors with non‐fused ring chemical structures. By introducing different functional atoms/groups into the para ‐position of phenyl in the OPT units, three non‐fused ring acceptors (NFREAs), C8‐2F, FC8‐2F and MeC8‐2F, were synthesized. The absorption spectrum of the three acceptors can be extended to about 950 nm with band‐gaps of 1.28—1.32 eV due to the strong electron donating ability of OPT. The frontier molecular orbital distribution of OPT based molecules obtained by quantum chemistry calculation results reveals that their energy alignment can be finely tuned to meet different requirements. Moreover, by changing the substituents on the OPT units, their Flory‐Huggins interaction parameter ( χ ) with the donor will be greatly influenced and different phase separation behavior can be accomplished. After blended with PBDB‐TF, the FC8‐2F‐based cell yields short circuit current density ( J sc ) of 23.21 mA·cm –2 , fill factor (FF) of 72.11% and the highest power conversion efficiency (PCE) of 12.42%. This work provides a new pathway for molecular design of new NFREAs, and demonstrates the application potential of OPT unit in realizing low band‐gap photovoltaic materials.