Unraveling the effect of two different polar solvents on the excited-state intramolecular proton transfer of 4'-methoxy-3-hydroxyflavone fluorescent dye.

Abstract

The fluorescence properties of 4'-methoxy-3-hydroxyflavone (M3HF) dye in different solvents were investigated through experimental (Phys. Chem. Chem. Phys., 2018, 20, 7885) and theoretical (Org. Chem. Front., 2019, 6, 218) methods. However, the intermolecular hydrogen bonds between M3HF and solvents were ignored. In this work, we investigated the effect of methanol (MeOH) and N,N-dimethylformamide (DMF) solvents on the excited-state intramolecular proton transfer (ESIPT) of M3HF fluorescent dye. In excited state (S1), the intramolecular hydrogen bonds are significantly strengthened, which can facilitate the ESIPT processes. The calculated absorption and fluorescence spectra agree well with the experimental date. The fluorescence spectra of M3HF and ESIPT tautomers (T⁎) were found to be sensitive to the solvent polarity. Upon photo-excitation, the electron density of the M3HF molecular is redistributed, which can provide driving force for the ESIPT. The polar solvents MeOH (hydrogen bond donor) and DMF (hydrogen bond acceptor) can form different types of intermolecular hydrogen bonds with M3HF. The two different bonding modes of intermolecular hydrogen bonds are expected to weaken the intramolecular hydrogen bond of M3HF to varying degrees. The analysis of the potential energy curves indicate that the ESIPT processes of M3HF can be hindered by the intermolecular hydrogen bonds. The intermolecular hydrogen bond of M3HF-DMF complex is weaker than that of M3HF-MeOH complex, while the potential barrier of the ESIPT process in DMF solvent is higher than that of in the MeOH solvent. This is principally because, in DMF solvent, the hydroxyl group H1 atom of M3HF can be captured by the O3 atom of DMF and form O3H1 bond with O3 atom in the intermediate process of ESIPT. There appears an energy barrier hopping point on the potential energy curve of M3HF in DMF solvent but does not appear in MeOH solvent.