Solvatochromism in Perylene Diimides; Experiment and Theory

We report an experimental and computational investigation into the solvatochromism of a perylene diimide derivative. The alkyl swallowtail substituents allowed solubility in many solvents of widely differing polarity, with a complicated resultant behaviour, illustrating both negative and positive solvatochromism as a function of dielectric constant. Luminescence quantum yield and optical absorption linewidth displayed an inverse correlation, indicating varying degrees of intermolecular aggregation, and a remarkably similar trend was found between the peak absorption wavelength and the solvent boiling point, illustrating the dependency of aggregation on the solvent interactions. These outline trends may be parameterised by an empirically derived dimensionless quantity, as a tool to be used in more sophisticated future models of solvatochromism in small molecule chromophores