ESIPT-induced spin–orbit coupling enhancement leads to tautomer fluorescence quenching of the 10-HHBF molecule

Abstract

We present novel insights into the interplay between excited state intramolecular proton transfer (ESIPT) and spin–orbit coupling (SOC) in the 10-hydroxy-11H-benzo[b]fluoren-11-one (10-HHBF) molecule, utilizing the time-dependent density functional theory approach and femtosecond transient absorption spectroscopy. Our discoveries entail a reassessment of the luminescence mechanism for 10-HHBF, characterizing it as an ESIPT fluorophore. Additionally, we demonstrate that the molecule undergoes intersystem crossing (ISC) following proton transfer, which quenches the fluorescence of the proton-transferred state, thus resulting in the absence of dual emission and a limited spectral range of fluorescence. Furthermore, our investigation reveals that 10-HHBF displays an SOC enhancement feature induced by ESIPT, which facilitates the ISC process. This trait serves as a barrier to the application of 10-HHBF in single-molecule white light emitters (SMWLEs). Our findings underscore the notable influence of the ESIPT-induced spin–orbit interaction enhancement on luminescent properties, which necessitates consideration in the design of SMWLEs.