Solvent effects on the ESIPT emission of salicylaldehyde Schiff base derivative: A theoretical reconsideration

[Display omitted] •The luminescence mechanism of DDHAC molecules in n-hexane and acetonitrile solvents was reconsidered.•The dual fluorescence peaks in n-hexane are ascribed to open-enol* and hydrogen-bonded enol*.•The single-peaked broad emission band in acetonitrile is formed by the combination of hydrogen-bonded enol* and keto*.•The reduced charge coupling of the keto* form is the reason for the non-fluorescence of keto* form in n-hexane solvent. Salicylaldehyde Schiff base derivatives have potential applications in bioimaging, chemical sensors and organic luminescence materials because of their high fluorescence quantum yield with the excited-state intramolecular proton transfer (ESIPT) process. Recently, Shu et al. studied the luminescent mechanism of the Et2N-substituted salicylaldehyde Schiff base compound (DDHAC) in solvents [Dyes and Pigments 195 (2021) 109708]. It showed double-peaked bands in an n-hexane solvent but a single-peaked band in an acetonitrile solvent. They suggested that the open-enol in the acetonitrile solvent was the dominant species. They considered that open-enol fluorescence and ESIPT fluorescence constituted a dual fluorescent phenomenon in the n-hexane solvent. However, because acetonitrile is a non-protonic solvent, DDHAC molecules in acetonitrile mainly existed as the lower-energy hydrogen-bonded enol form rather than the open-enol form alone. In addition, the open-enol did not undergo the ESIPT process in n-hexane. Therefore, the luminescence mechanism of the DDHAC molecules in n-hexane and acetonitrile solvents needs to be reconsidered. In this study, we investigated the DDHAC molecules in n-hexane and acetonitrile solvents using the density functional theory and time-dependent density functional theory. The potential energy surfaces and optimisation of structures elucidated that the DDHAC molecules in n-hexane and acetonitrile solvents underwent the ESIPT process. The calculated fluorescence peaks demonstrated that the single-peaked broad emission band in the acetonitrile solvent was formed by the combination of the hydrogen-bonded enol* and keto* forms rather than open-enol*. Moreover, the dual fluorescence peaks in the n-hexane solvent were reattributed to the open-enol* form and hydrogen-bonded enol* form. The lack of keto* fluorescence in the n-hexane solvent was attributed to diminished charge coupling in comparison to the enol* form. Our results revise the mechanism of the DDHAC molecules in n-hexane and acetonitr