Unveiling the influence of atomic electronegativity on the double ESIPT processes of uralenol: a theoretical study

Abstract In this work, the effects of atomic electronegativity (O, S, and Se atoms) on the competitive double excited-state intramolecular proton transfer (ESIPT) reactions and photophysical characteristics of uralenol (URA) were systematically explored by using the density functional theory (DFT) and time-dependent DFT (TD-DFT) methods. The calculated hydrogen bond parameters, infrared (IR) vibrational spectra, reduced density gradient (RDG) scatter plots, interaction region indicator (IRI) isosurface and topology parameters have confirmed the six-membered intramolecular hydrogen bond (IHB) O4-H5…O3 is the stronger one in all the three studied compounds. Subsequently, frontier molecular orbitals (FMOs) and natural bond orbital (NBO) population analysis essentially uncover that the electron redistribution has induced the ESIPT process. Besides, the constructed potential energy curves (PECs) have indicated that the ESIPT process prefers to occur along the O4-H5…O3 rather than the O1-H2…O3 and the proton-transfer energy barrier is gradually decreased with the weakening of atomic electronegativity from URA to URA-S and URA-Se. In a conclusion, the attenuating of atomic electronegativity has enhanced the IHBs of URA and thereby promoting the ESIPT reaction, which is helpful for further developing novel fluorophores based on ESIPT behavior in the future.