Neutral vs Charged Luminescent Radicals: Anti-Kasha Emission and the Impact of Molecular Surrounding

Organic luminescent materials attract growing interest as an elegant solution for sustainable and inexpensive light-emitting devices. Most of them are neutral-emitting molecules with an implicit restriction of 25% internal quantum efficiency due to a spin-forbidden nature of the T₁ → S₀ transition. Utilizing organic radicals allows one to overcome such limits by theoretically boosting quantum yield up to 100%. Recently, different light-emitting radicals based on carbonyl- and carboxyl-substituted benzenes were synthesized and stabilized in different polymer matrices or ionic liquids. While some of them were proved to be suitable luminescent materials, the exact theoretical explanation of the nature of their emission is missing. There are two main hypotheses proposed in the literature. The first one suggests that the origin of luminescence is D₂ → D₀ anti-Kasha emission from anion radicals, while the second theory is based on D₁ → D₀ Kasha emission from neutral protonated radicals. In this work, we investigate both hypotheses and compare their derivatives with the available experimental data. We used density functional theory and complete-active space perturbation theory to investigate the absorption and emission properties in various aromatic carbonyl radicals. We found that both emission mechanisms can coexist simultaneously, with a dominant emission contribution made by anion radicals because of better agreement between oscillator strengths and radiative rate constants. Our numerical simulations agree with the experimental data and provide theoretical foundations for the fabrication of next-generation light-emitting devices based on luminescent radicals.