The simplest structure of a stable radical showing high fluorescence efficiency in solution: benzene donors with triarylmethyl radicals

Abstract

Donor–radical acceptor systems have recently attracted much attention as efficient doublet emitters that offer significant advantages for applications such as OLEDs. We employed an alkylbenzene (mesityl group) as the simplest donor to date and added it to a diphenylpyridylmethyl radical acceptor. The (3,5-difluoro-4-pyridyl)bis[2,6-dichloro-4-(2,4,6-trimethylphenyl)phenyl]methyl radical (Mes₂F₂PyBTM) was prepared in only three steps from commercially available reagents. A stable radical composed of only one pyridine ring, four benzene rings, methyl groups, halogens, and hydrogens showed fluorescence of over 60% photoluminescence quantum yield (PLQY) in chloroform, dichloromethane, and PMMA. The key to high fluorescence efficiency was benzene rings perpendicular to the diphenylpyridylmethyl radical in the doublet ground (D₀) state. The relatively low energy of the β-HOMO and the electron-accepting character of the radical enabled the use of benzenes as electron donors. Furthermore, the structural relaxation of the doublet lowest excited (D₁) state was minimized by steric hindrance of the methyl groups. The reasons for this high efficiency include the relatively fast fluorescence transition and the slow internal conversion, both of which were explained by the overlap density between the D₁ and D₀ states.