Electronic spectra and intersystem spin‐orbit coupling in 1,2‐ and 1,3‐squaraines

The main photophysical properties of a series of recently synthetized 1,2‐ and 1,3‐squaraines, including absorption electronic spectra, singlet‐triplet energy gaps, and spin‐orbit matrix elements, have been investigated by means of density functional theory (DFT) and time‐dependent DFT approaches. A benchmark of three exchange‐correlation functionals has been performed in six different solvent environments. The investigated 1,2 squaraines have been found to possess two excited triplet states (T₁ and T₂) that lie below the energy of the excited singlet one (S₁). The radiationless intersystem spin crossing efficiency is thus enhanced in both the studied systems and both the transitions could contribute to the excited singlet oxygen production. Moreover, they have a singlet‐triplet energy gap higher than that required to generate the cytotoxic singlet oxygen species. According to our data, these compounds could be used in photodynamic therapy applications that do not require high tissue penetration. © 2014 Wiley Periodicals, Inc.