Fine-tuning directionality of ESIPT behavior of the asymmetric two proton acceptor system via atomic...

The excited state intramolecular proton transfer (ESIPT) processes and photophysical features of 3-(benzo[d]oxazol-2-yl)-2-hydroxy-5-methoxy benzaldehyde (BOHMB) and 3-(benzo[d]selenazole-2-yl)-2-hydroxy-5-methoxy benzaldehyde (BSeHMB) molecules were investigated in detail by using density functional theory (DFT) and time-dependent DFT (TD-DFT) methods. The strengthened excited state hydrogen bonds (H-bond) of the title compounds are favorable to ESIPT process according to the analyses of structural parameter, infrared vibration frequency, electron density and reduced density gradient. The atomic substitution changes the intramolecular H-bond O₁-H₂…O₃ and O₁-H₂…N₄ and the fluorescence emission peaks of BOHMB-N and BSeHMB-N in normal and tautomer forms. The potential energy curves indicate that the ESIPT energy barriers of BOHMB-O, BTHMB-O and BSeHMB-O increase as the electron-withdrawing abilities of atoms (from O to S and Se) are gradually weakened. However, the ESIPT energy barriers of BOHMB-N and BTHMB-N follow the totally opposite order. For BOHMB and BSeHMB, ESIPT process prefers to occur in the direction from O-H group to the O atom.