Influence of Large Steric Hinderance Substituent Position on Conformation and Charge Transfer Process for Non‐Fused Ring Acceptors

To obtain stable and planar molecular geometry in non-fused electron acceptors, A4T-25 and A4T-26 are designed and synthesized by introducing the bulk 2,4,6-triisopropylphenyl side groups onto different positions of the central two thiophene units. A4T-25 and A4T-26 both show a narrow-bandgap of 1.39 and 1.46 eV, with highest occupied molecular orbital/lowest unoccupied molecular orbital levels of -5.56/-3.81 and -5.65/-3.83 eV, respectively, and the electrostatic potential distributions imply that they have strong electron-accepting capability. The single crystal structure analysis and the transfer integral calculation demonstrate that the much more compact π-π stacking in A4T-26 can promote efficient charge transportation compared to that in A4T-25. Therefore, the electron mobility of A4T-26 is obviously higher and more balanced than that of A4T-25. When blending the two acceptors with the same polymer donor PBDB-TF, the photovoltaic cell based on PBDB-TF:A4T-25 has an inadequate power conversion efficiency (PCE) of 7.83%, while the PBDB-TF:A4T-26-based one yields an enhanced PCE of 12.1%. Overall, this study offers an insight into the relationship between the fine-tuning of the molecular structure of non-fused ring acceptors and the corresponding charge transfer process in organic solar cells.