The excited-state intramolecular proton transfer in NH-type dye molecules with a seven-membered-ring intramolecular hydrogen bond: A theoretical insight

Excited-state intramolecular proton transfer (ESIPT) reactions of a series of N(R)H⋯N-type seven-membered-ring hydrogen-bonding compounds were explored by employing density functional theory/time-dependent density functional theory calculations with the PBE0 functional. Our results indicate that the absorption and emission spectra predicted theoretically match very well the experimental findings. Additionally, as the electron-withdrawing strength of R increases, the intramolecular H-bond of the NS₁ form gradually enhances, and the forward energy barrier along the ESIPT reaction gradually decreases. For compound 4, its ESIPT reaction is found to be a barrierless process due to the involvement of a strong electron-withdrawing COCF₃ group. It is therefore a reasonable presumption that the ESIPT efficiency of these N(R)H⋯N-type seven-membered-ring H-bonding systems can be improved when a strong electron-withdrawing group in R is introduced.