Dinuclear Cu(I) Complex with Combined Bright TADF and Phosphorescence. Zero-Field Splitting and Spin–Lattice Relaxation Effects of the Triplet State

The three-fold bridged dinuclear Cu(I) complex Cu2(μ-I)2(1N-n-butyl-5-diphenyl-phosphino-1,2,4-triazole)3, Cu2I2(P^N)3, 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 (S1)–triplet (T1) energy gap is as small as only 430 cm–1 (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 T1 into substates by ∼2.5 cm–1 (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.