Thermally activated delayed fluorescence has been found in a group of tricarbazolylamines that are purely electrondonating, non-charge-transfer (CT) molecules. We show that the reverse intersystem crossing step in these materials is mediated through upper triplet states. Reverse internal conversion is shown to be the thermally activated mechanism behind the triplet harvesting mechanism. The strongly mixed n−π*/π−π* character of the lowest energy optical transitions retains high oscillator strength and gives rise to high Φ PL . Organic light-emitting diode devices using these materials were fabricated to show very narrow (full width at half-maximum = 38−41 nm) electroluminescence spectra, clearly demonstrating the excitonic nature of the excited states. This new combination of physicochemical properties of a non-CT molecule yields thermally activated delayed fluorescence, but via a different, physical mechanism, reverse internal conversion delayed fluorescence.
Thianthrenes have been nearly forgotten as phosphors in recent years, but are now coming back, showing their strong potential in luminescent applications. Here, we present a comprehensive photophysical study of a carbazolyl derivative of thianthrene in different matrices and environments. The diffusion of oxygen is slowed down in the rigid environment of thianthrene organic crystals suppressing their phosphorescence quenching, as well as triplet-triplet annihilation. This facilitates the observation of simultaneous fluorescence and phosphorescence emissions at room temperature, in air, giving origin to strong white luminescence. Moreover, the color coordinates of the dual fluorescence-phosphorescence white emission, which is observed only in rigid amorphous media and in crystals, can be tuned.
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