Application of the Heavy-Atom Effect for (Sub)microsecond Thermally Activated Delayed Fluorescence and an All-Organic Light-Emitting Device with Low-Efficiency Roll-off

The feature of abundant and environmentally friendly heavy atoms (HAs) like bromine to accelerate spin-forbidden transitions in organic molecules has been known for years. In combination with the easiness of incorporation, bromine derivatives of organic emitters showing thermally activated delayed fluorescence (TADF) emerge as a cheap and efficient solution for the slow reverse intersystem crossing (rISC) problem in such emitters and strong efficiency roll-off of all-organic light-emitting diodes (OLEDs). Here, we present a comprehensive photophysical study of a tri-PXZ-TRZ emitter reported previously and its hexabromo derivative showing a remarkable enhancement of rISC of up to 9 times and a short lifetime of delayed fluorescence of 2 mu s. Analysis of the key molecular vibrations and TADF mechanism indicates almost compete blockage of the spin-flip transition between the charge-transfer states of different multiplicity (CT)-C-3 -> (CT)-C-1. In such a case, rISC as well as its enhancement by the HA is realized via the (LE)-L-3 -> (CT)-C-1 transition, where (LE)-L-3 is the triplet state localized on the same brominated phenoxazine donor involved in the formation of the (CT)-C-1 state. Interestingly, the spin-orbit coupling (SOC) with two other (LE)-L-3 states is negligible because they are localized on different donors and not involved in (CT)-C-1. We consider this as an example of an additional "localization" criterion that completes the well-known El Sayed rule on the different nature of states for nonzero SOC. The applicative potential of such a hexabromo emitter is tested in a "hyperfluorescent" system containing a red fluorescent dopant (tetraphenyldibenzoperiflanthene, DBP) as an acceptor of F & ouml;rster resonance energy transfer, affording a narrow-band red-emitting system, with most of the emission in the submicrosecond domain. In fact, the fabricated red OLED devices show remarkable improvement of efficiency roll-off from 2-4 times depending on the luminance, mostly because of the increase of the rISC constant rate and the decrease of the overall delayed fluorescence lifetime thanks to the HA effect.