Phosphorescent Cationic Heterodinuclear Ir ^III /M ^I Complexes (M=Cu ^I , Au ^I ) with a Hybrid Janus‐Type N‐Heterocyclic Carbene Bridge

A novel class of phosphorescent cationic heterobimetallic IrIII /MI complexes, where MI =CuI (4) and AuI (5), is reported. The two metal centers are connected by the hybrid bridging 1,3-dimesityl-5-acetylimidazol-2-ylidene-4-olate (IMesAcac) ligand that combines both a chelating acetylacetonato-like and a monodentate N-heterocyclic carbene site coordinated onto an IrIII and a MI center, respectively. Complexes 4 and 5 have been prepared straightforwardly by a stepwise site-selective metalation with the zwitterionic [(IPr)MI (IMesAcac)] metalloproligand (IPr=1,3-(2,6-diisopropylphenyl)-2H-imidazol-2-ylidene) and they have been fully characterized by spectroscopic, electrochemical, and computational investigation. Complexes 4 and 5 display intense red emission arising from a low-energy excited state that is located onto the "Ir(C^N)" moiety featuring an admixed triplet ligand-centered/metal-to-ligand charge transfer (3 IL/1 MLCT) character. Comparison with the benchmark mononuclear complexes reveals negligible electronic coupling between the two distal metal centers at the electronic ground state. The bimetallic systems display enhanced photophysical properties in comparison with the parental congeners. Noteworthy, similar non-radiative rate constants have been determined along with a two-fold increase of radiative rate, yielding brightly red-emitting cyclometalating IrIII complexes. This finding is ascribed to the increased MLCT character of the emitting state in complexes 4 and 5 due to the smaller energy gap between the 3 IL and 1 MLCT manifolds, which mix via spin-orbit coupling.