Synthesis, Structure, and Photophysical Properties of Two Four-Coordinate CuI–NHC Complexes with Efficient Delayed Fluorescence

Two luminescent cationic heteroleptic four-coordinate CuI complexes supported by N-heterocyclic carbene ligand and diphosphine ligand were successfully prepared and characterized. These complexes adopt typical distorted tetrahedral configuration and have high stability in solid state. Quantum chemical calculations show carbene units have contributions to both highest occupied molecular orbitals and lowest unoccupied molecular orbitals of these CuI–NHC complexes, the lowest-lying singlet and triplet excitations (S0 → S1 and S0 → T1) of [Cu­(Pyim)­(POP)]­(PF6) are dominated by metal-to-ligand charge transfer (MLCT) transition, while the S0 → S1 and S0 → T1 excitations of [Cu­(Qbim)­(POP)]­(PF6) are mainly MLCT and ligand-centered transitions, respectively. These CuI–NHC complexes show efficient long-lifetime emissions (λem = 520 nm, τ = 79.8 μs, Φ = 0.56 for [Cu­(Pyim)­(POP)]­(PF6), λem = 570 nm, τ = 31.97 μs (78.99%) and 252.2 μs (21.01%), Φ = 0.35 for [Cu­(Qbim)­(POP)]­(PF6)) in solid state at room temperature, which are confirmed as delayed fluorescence by investigating the emissions at 77 K.