Accurate theoretical prediction of optical properties of BODIPY dyes

Boron‐dipyrromethene dyes (BODIPY) are of great interest nowadays mostly due to their valuable optical properties. Nevertheless, no systematic research of the optical property dependence on the structure of dyes has been performed yet. In this work, analysis of the available quantum‐chemical methods for BODIPY optical property calculations has been carried out. The accuracy of eight DFT functionals has been studied. The solvation effects upon excitation have been considered within two schemes. The methods that predict the absorption and emission spectra of BODIPY derivatives with high accuracy have been proposed. Using the suggested methods, the influence of nature of substituents and their position in the BODIPY core on the optical spectra of the dyes has been studied. A complex pattern of red‐ and blue‐shifts in optical spectra in dependence of nature and position of substituents has been revealed. The results of this work provide the way for efficient design of BODIPY derivatives with desired optical properties. Absorption and emission spectra of BODIPY dyes in solution were studied using TD‐DFT. M062X in LR‐scheme and wB97XD in SS‐scheme are found to be the most accurate for prediction of absorption and emission spectra of BODIPY. Substituents’ influence on the optical spectra of the dyes was systematically studied. Key role of π‐electron delocalization on the optical properties was observed. Results of the work provide the way to rational design of new BODIPY structures with desired optical properties.