Theoretical predictions of the spectroscopic properties of BODIPY dyes: Effects of the fused aromatic and heteroaromatic rings at the b, g bonds

[Display omitted] •We computationally study absorption and fluorescence properties of b, g-fused BODIPY.•We show that the b, g-fused dyes have the excited states of the LE- and CT-type.•We explain effects of b, g-fused aromatics in the BODIPY core on optical properties. The fusion of aryl and heteroaryl moieties in the BODIPY skeleton is the important route to design BODIPYs exhibiting absorption and fluorescence in red or near infra-red regions. Despite the importance of this approach, little is known about the influence of aryl and heteroaryl rings on the position of the energy levels of the lower electronic states of such dyes. In this paper, the influence of benzene (B), thiophene (T) and furan (F) rings fused in the BODIPY core (b) at both b and g bonds on the optical properties of the symmetric BbB, TbT and FbF and asymmetric TbF, BbF and BbT dyes have been investigated by TD-CAM-B3LYP and RI-CC2 calculations. We have shown that in contrast to the locally excited (LE0-type) main vertical state, energy of which is nearly the same for all the substituents at the b and g bonds, energy of the next two states of the LE1- and LE2-type for the symmetric dyes or the charge transfer (CT1- and CT2-type) for the asymmetric dyes depends strongly on the nature of the rings at the b and g bonds. The benzene-fused dyes (BbF, BbT, BbB) have the lowest energy of the excited levels of the LE-type (or CT1-type) states, and inversion with LE0-type levels occurs. As a result, the dramatic decrease of the fluorescence quantum yield is expected in these cases. The identification of these effects provides a quality framework for understanding of how fused substituents regulate photophysical processes of BODIPYs.