A new interpretation of the ESIPT mechanism of 2-(benzimidazol-2-yl)-3-hydroxychromone derivatives

Abstract The present study demonstrates the excited-state intramolecular proton transfer (ESIPT) mechanism of 2-(benzimidazol-2-yl)-3-hydroxychromone (DH3B2) is based on density functional theory (DFT) and time-dependent density functional theory (TDDFT) methods. We find that DH3B2-C is the main conformation to occur ESIPT. Moreover, we get the different results of DH3B2 for the ESIPT mechanisms in comparison with the previous reports. We have optimized three isomers (DH3B2-A, DH3B2-B and DH3B2-C), and calculated absorption and fluorescence spectra, which agree well with the experimental data. Furthermore, we prove the hydrogen bond is enhanced in the S 1 state by comparing infrared vibrational spectra, the relevant bond length and bond angle. In our calculations, the results of the three levels of calculations (CAM-B3LYP/TZVP, B3LYP/TZVP and PBEPBE/TZVP) indicate that DH3B2-C is the most stable conformation, by compared the single point energy of three isomers. By constructed the potential energy surfaces (PESs), we find the converted relationship among the three isomers; DH3B2-C is the main conformation in which DH3B2 exists. Furthermore, combination with reduced density gradient (RDG) function, the hydrogen bond of DH3B2-C is stronger than that of DH3B2-A and DH3B2-B, which proves that DH3B2-C form is the most favorable form for ESIPT among the three isomers. Meanwhile, we have further investigated the ESIPT mechanisms of DH3B2, via constructing the potential energy curves (PECs). These results have shown that DH3B2-C is easier to ESIPT occur than DH3B2-A and DH3B2-B. Therefore, the proton receptors of the ESIPT are mainly the benzimidazole nitrogen atoms.