Side-Chain Engineering for Regulating Structure and Properties of a Novel Visible-Light-Driven Perylene Diimide-based Supramolecular Photocatalyst

Systematic and in-depth explorations of the effects of side-chain modulation on the molecular assembly, optoelectronic properties, and photocatalytic properties of supramolecular systems, as well as the kinetics of charge separation and migration in these systems, are rare. In this study, a novel supramolecular photocatalyst with an alkoxy side chain (S-EPDI) was successfully developed through subtle design of the short and linear alkoxyl side chains, affording a phenol degradation efficiency approximately four times that of the counterpart with an alkyl side chain (S-APDI). Notably, combined density functional theory (DFT) calculations, absorption spectroscopy, and other characterizations revealed that the perylene diimide (PDI) molecular units, through π-π stacking, formed a unique rotationally offset stacked supramolecular structure, exhibiting a significant dipole moment. This gave rise to the formation of a larger inherent electric field within S-EPDI compared to S-APDI. Moreover, the study quantitatively demonstrated that a stronger inherent electric field and lower rate of surface charge recombination facilitate efficient separation of the photogenerated carriers. Therefore, the side-chain molecular engineering method employed in this study offers an effective approach for modulating the kinetics of charge migration.