Dielectric environment effects on rylene-based organic fluorophores: A quantum mechanical study

Rylene derivatives are known for their strong fluorescence, large absorption coefficients, and outstanding thermal and photo-stability. We report quantum-mechanical (QM) calculations of various Lumogen® dyes encapsulated within core-stabilized micelles. Theoretical methods were employed to calculate dyes' absorption wavelengths, including time-dependent density functional theory and configuration interaction methods with implicit solvation models. Then, the calculated absorption spectra were compared with experimental ones. We observed absorption wavelength shifts correlated with structural features of dyes and solvents identified from QM calculations and statistical analysis. Such structural insights enabled the prediction of absorption characteristics of rylene-based materials in various dielectric environments by developing regression models.