Effect of methyl substituents on the electronic transitions in simple meso-aniline-BODIPY based dyes: RI-CC2 and TD-CAM-B3LYP computational investigation.

The S→S, i=1-5 electronic transitions of four 8-(4-aniline)-BODIPY and four 8-(N,N-dimethyl)-BODIPY dyes, differ by number and position of methyl substituents in the BODIPY frame, were investigated theoretically using ab initio the coupled cluster doubles (CC2) and TD-CAM-B3LYP methods. Methyl substituents in the BODIPY frame and the aniline fragment at the meso position disturb energy of local excitations S→S, S→S, and S→S weakly in comparison with the fully unsubstituted BODIPY molecule. These transitions in experimental spectra form the most long-wave absorption bands at ca. 500nm as well as absorption bands in the region of 300-400nm. At the same time, the presence of aniline fragments leads to the appearance of new S→S transitions of the charge transfer character in electronic spectra of BODIPYs. We also found a linear relationship between vertical energy of these charge transfer transitions and the electron donating power of an aniline fragment and electron accepting power of the BODIPY core depending on the number and position of methyl groups. The CC2 method provides the best overall description of the excitation energies in line with the experimental observations. On average, the quality of TD-CAM-B3LYP is almost equal to that of CC2, however the TD method with the CAM-B3LYP functional slightly underestimates the CT excitation energy.