Bright green PhOLEDs using cyclometalated diiridium(III) complexes with bridging oxamidato ligands as phosphorescent dopants

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 (ΔΛ) and the racemic form consisting of two enantiomers (ΔΔ and ΛΛ)-with anti-oxamidato bridges. The precursor μ-dichloro-bridged complex 4 is very weakly emissive in solution, whereas the oxamidato bridged complexes 5 and 6 are highly emissive (ΦPL 73% and 63%) with short excited state lifetimes of τP 0.84 and 1.16 μs, 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 (Lmax > 25 000 cd m-2) for diiridium complexes.