Three States Involving Vibronic Resonance is a Key to Enhancing Reverse Intersystem Crossing Dynamics of an Organoboron-Based Ultrapure Blue Emitter

The recently developed narrow-band blue-emitting organoboron chromophores based on the multiple-resonance (MR) effect have now become one of the most important components for constructing efficient organic light emitting diodes (OLEDs). While they basically emit through fluorescence, they are also known for showing substantial thermally activated delayed fluorescence (TADF) even with a relatively large singlet-triplet gap (Delta E-ST). Indeed, understanding the reverse intersystem crossing (RISC) dynamics behind this peculiar TADF will allow judicious molecular designs toward achieving better performing OLEDs. Explaining the underlying nonadiabatic spin-flip mechanism, however, has often been equivocal, and how the sufficiently fast RISC takes place even with the sizable Delta E(ST )and vanishingly small spin-orbit coupling is not well understood. Here, we show that a vibronic resonance, namely the frequency matching condition between the vibration and the electronic energy gap, orchestrates three electronic states together and this effect plays a major role in enhancing RISC in a typical organoboron emitter. Interestingly, the mediating upper electronic state is quite high in energy to an extent that its thermal population is vanishingly small. Through semiclassical quantum dynamics simulations, we further show that the geometry dependent non-Condon coupling to the upper triplet state that oscillates with the frequency Delta E-ST(/h) is the main driving force behind the peculiar resonance enhancement. The existence of an array of vibrational modes with strong vibronic rate enhancements provides the ability to sustain efficient RISC over a range of Delta E-ST in defiance of the energy gap law, which can render the MR-emitters peculiar in comparison with more conventional donor-acceptor type emitters. Our investigation may provide a new guide for future blue emitting molecule developments.

Automated summary

The development of narrow-band blue-emitting organoboron chromophores based on the multiple-resonance (MR) effect has become essential for constructing efficient organic light-emitting diodes (OLEDs). These chromophores exhibit a combination of fluorescence and thermally activated delayed fluorescence (TADF), with a unique reverse intersystem crossing (RISC) mechanism enhancing their performance. The presence of vibronic resonance and strong vibronic rate enhancements in these chromophores allows for efficient RISC over a range of singlet-triplet energy gaps (Delta E-ST), making them stand out compared to conventional donor-acceptor emitters.