Abstract
In contrast to monoiridium complexes, the study of diiridium complexes as dopants in phosphorescent organic light-emitting devices (PhOLEDs) is largely unexplored. We now describe the syntheses, detailed NMR analyses, X-ray crystal structures and optoelectronic properties of the new cyclometalated diiridium complexes 5 and 6 in which the iridium centres are bridged by oxamidato ligands. These complexes contain diastereomers -the meso form (DL) and the racemic form consisting of two enantiomers (Delta Delta and Lambda Lambda) -with anti-oxamidato bridges. The precursor mu-dichloro-bridged complex 4 is very weakly emissive in solution, whereas the oxamidato bridged complexes 5 and 6 are highly emissive (FPL 73% and 63%) with short excited state lifetimes of tau(P) 0.84 and 1.16 mu s, respectively. Cyclic voltammetry studies demonstrate that the oxamidato bridging ligand plays a role in mediating intramolecular interactions between the iridium centres. Density functional theory (DFT) calculations and time dependent-DFT (TD-DFT) calculations provide further insights into the structural, electronic, and photophysical properties of the complexes in their ground and excited states. Phosphorescent organic light-emitting diodes (PhOLEDs) using complexes 5 and 6 as the emissive dopants in a simple architecture using a solution-processed active layer give bright green electroluminescence with remarkably high luminance (L-max > 25 000 cd m(-2)) for diiridium complexes.