Hot Vibrational States in a High-Performance Multiple Resonance Emitter and the Effect of Excimer Quenching on Organic Light-Emitting Diodes

[Image: see text] The photophysics of multiple resonance thermally activated delayed fluorescence molecule ν-DABNA is described. We show coupling of a 285 cm(–1) stretching/scissoring vibrational mode of peripheral phenyl rings to the S(1) state, which dictates the ultimate emission full-width at half maximum. However, a separate high amplitude mode, 945 cm(–1) of the N-biphenyl units, mediates the reverse intersystem crossing (rISC) mechanism. Concentration-dependent studies in solution and solid state reveal a second emission band that increases nonlinearly with concentration, independent of the environment assigned to excimer emission. Even at concentrations well below those used in devices, the excimer contribution affects performance. Using different solvents and solid hosts, rISC rates between 3–6 × 10(5) s(–1) are calculated, which show negligible dependence on environmental polarity or host packing. At 20 K over the first 10 ns, we observe a broad Gaussian excimer emission band with energy on-set above the S(1) exciton band. An optical singlet-triplet gap (ΔE(ST)) of 70 meV is measured, agreeing with previous thermal estimates; however, the triplet energy is also found to be temperature-dependent. A monotonic increase of the exciton emission band full-width at half maximum with temperature indicates the role of hot transitions in forming vibrational excited states at room temperature (RT), and combined with an observed temperature dependency of ΔE(ST), we deduce that the rISC mechanism is that of thermally activated reverse internal conversion of T(1) to T(N) (n ≥ 2) followed by rapid rISC of T(N) to S(1). Organic light-emitting diodes with ν-DABNA as a hyperfluorescent emitter (0.5 wt % and 1 wt %) exhibit an increase of maximum external quantum efficiency, reaching 27.5% for the lower ν-DABNA concentration. On the contrary, a Förster radius analysis indicated that the energy transfer ratio is smaller because of higher donor–acceptor separation (>2.4 nm) with weak sensitizer emission observed in the electroluminescence. This indicates excimer quenching in 1 wt % devices.