Development of fluorinated benzils and bisbenzils as room-temperature phosphorescent molecules

Abstract

Pure organic phosphorescent molecules are attractive alternatives to transition-metal-complex-based phosphores for biomedical and technological applications owing to their abundance and nontoxicity. This article discloses the design, synthesis, and photophysical properties of fluorinated benzil and bisbenzil derivatives as potential pure organic room-temperature phosphorescent molecules. These compounds were separately converted from the corresponding fluorinated bistolanes via PdCl₂-catalyzed oxidation by dimethyl sulfoxide, while nonfluorinated bistolane provided the corresponding bisbenzil derivatives exclusively in a similar manner. Intensive investigations of the photophysical properties of the benzil and bisbenzil derivatives in toluene at 25 °C showed both fluorescence with a photoluminescence (PL) band at a maximum wavelength (λ_PL) of around 400 nm and phosphorescence with a PL band at a λ_PL of around 560 nm. Interestingly, intersystem crossing effectively caused fluorinated benzils to emit phosphorescence, which may arise from immediate spin-orbit coupling involving the ¹(n, π)→³(π, π) transition, unlike the case of fluorinated or nonfluorinated bisbenzil analogues. These findings offer a useful guide for developing novel pure organic room-temperature phosphorescent materials.

Keywords: alkyne oxidation; benzils; bistolanes; fluorinated compounds; phosphorescence.