The influence of intermolecular hydrogen bonds on single fluorescence mechanism of 1-hydroxy-11H-benzo [b]fluoren-11-one and 10-hydroxy-11H-benzo [b]fluoren-11-one.

Solvent effects usually have an essential effect on excited-state intramolecular proton transfer (ESIPT) processes and fluorescence mechanism. This contribution presents new insights into a newly synthesized compound, namely, 10-hydroxy-11H-benzo [b]fluoren-11-one (10-HHBF), and its analogue 1-hydroxy-11H-benzo [b]fluoren-11-one (1-HHBF), which exhibit single-fluorescence properties in protic solvents (methanol, MeOH), using time-dependent density functional theory (TDDFT). The results established four schemes, namely, MeOH-1, MeOH-2, MeOH-3, and MeOH-4, for 1-HHBF and 10-HHBF in MeOH. Absorption and emission spectra showed that the 1-HHBF and 10-HHBF at the conformation MeOH-2, MeOH-3 and MeOH-4 were closer to the experimental values than those at the MeOH-1. Energy barriers indicate the possibility of the ESIPT and ESPT process in 1-HHBF and 10-HHBF under the four schemes. Moreover, reverse PT processes were easy to occur at the conformations of MeOH-2, MeOH-3, and MeOH-4 in the S state. Given the single-fluorescence properties of 1-HHBF and 10-HHBF in the experiment, the conformation MeOH-1 was excluded. Therefore, our contribution proved that MeOH-2, MeOH-3, and MeOH-4 might exist in single fluorescence, and the hydrogen bond at the MeOH-2 position plays a decisive role, indicating the intermolecular hydrogen bonding interaction on the acceptor atom will have a more significant impact on the fluorescence properties of the substance.