Spin-spin interactions in organic light-emitting diodes (OLEDs) based on thermally activated delayed fluorescence (TADF) are important because radiative recombination is largely determined by triplet-to-singlet conversion, also called reverse intersystem crossing (RISC). Less obvious is the fact that the non-emissive triplet states are spin-polarized, e.g., by charge injection, and spin-selection rules prevent part of the triplet population from RISC. To explore the relationship between these two processes, we apply a two-frequency spin-resonance technique, which is essentially spectral hole burning, that directly probes electroluminescence. This allows us not only to independently confirm high spin-polarization, but also to distinguish between individual triplet exciplex states distributed in the OLED emissive layer. These states can be decoupled from the heterogeneous nuclear environment as a source of spin dephasing and can even be coherently manipulated on a spin-spin relaxation time scale T2* of 30 ns. Furthermore, we obtain the characteristic spin-lattice relaxation time T1 of the triplet exciplex in the range of 50 us, which is longer than the RISC time. We conclude that long spin relaxation time rather than RISC is an efficiency-limiting step for intermolecular donor:acceptor systems. Finding TADF emitters with faster spin relaxation will benefit this type of TADF OLEDs.
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