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 4-5 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 spectroscopical, electrochemical and computational investigation. Complexes 4-5 display intense red emission arising from a low-energy lying excited state that is located onto the "Ir(C^N)" moiety featuring an admixed triplet ligand centered/metal-to-ligand charge transfer (3IL/1MLCT) 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 nonradiative rate constant has been determined along with a two-fold increase of radiative rate, yielding brightly red-emitting cyclometallating IrIII complexes. This finding is ascribed to the increased MLCT character of the emitting state in complexes 4-5 due to the smaller energy gap between the 3IL and 1MLCT manifolds, which mix via spin-orbit coupling.
Polo, Federico [Writing – Original Draft Preparation]
|Titolo:||Phosphorescent cationic heterodinuclear IrIII/MI complexes (M = CuI, AuI) with a hybrid Janus-type N-heterocyclic carbene bridge|
|Data di pubblicazione:||2020|
|Appare nelle tipologie:||2.1 Articolo su rivista |