The three-fold bridged dinuclear Cu(I) complex Cu(μ-I)(1 N- n-butyl-5-diphenyl-phosphino-1,2,4-triazole), CuI(P^N), shows bright thermally activated delayed fluorescence (TADF) as well as phosphorescence at ambient temperature with a total quantum yield of 85% at an emission decay time of 7 μs. The singlet (S)-triplet (T) energy gap is as small as only 430 cm (53 meV). Spin-orbit coupling induces a short-lived phosphorescence with a decay time of 52 μs ( T = 77 K) and a distinct zero-field splitting (ZFS) of T into substates by ∼2.5 cm (0.3 meV). Below T ≈ 10 K, effects of spin-lattice relaxation (SLR) are observed and agree with the size of ZFS. According to the combined phosphorescence and TADF, the overall emission decay time is reduced by ∼13% as compared to the TADF-only process. The compound may potentially be applied in solution-processed OLEDs, exploiting both the singlet and triplet harvesting mechanisms.
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