Highly Efficient Red-Emitting Bis-Cyclometalated Iridium Complexes.

Bis-cyclometalated iridium complexes with enhanced phosphorescence quantum yields in the red region of the visible spectrum are described. Here, we demonstrate that incorporating strongly π-donating, nitrogen-containing ß-ketoiminate (acNac), ß-diketiminate (NacNac), and N, N'-diisopropylbenzamidinate (dipba) ancillary ligands can demonstrably perturb the excited-state kinetics, leading to enhanced photoluminescence quantum yields (ΦPL) for red-emitting compounds. A comprehensive study of the quantum yields and lifetimes for these complexes reveals that for the compounds with the highest quantum yields, the radiative rate constant ( kr) is significantly higher than that of related complexes, and contributes substantially to the increase in ΦPL. Experimental and computational evidence is consistent with the notion that an increase in spin-orbit coupling, caused by an enhancement of the metal-to-ligand charge transfer (MLCT) character of the excited state via destabilization of the HOMO, is mainly responsible for the faster radiative rates. One of the compounds was shown to be effective as the emissive dopant in an organic light-emitting diode device.

Cyclometalated gold(III) trioxadiborrin complexes: studies of the bonding and excited states.

Trioxadiborrins are chelating ligands that assemble in dehydration reactions of boronic acids. They are structurally related to ß-diketonate ligands, but have a 2-charge. Little is known of the bonding properties of trioxadiborrin ligands. Presented here are density-functional theory (DFT) studies of cyclometalated gold(III) trioxadiborrins. Substituent effects are evaluated, and comparison is made to the cyclometalating 2-(4-tolyl)pyridine (tpy) ligand on gold. The tpy ligand binds more strongly than any trioxadiborrin ligand considered here, and the two ligands bind competitively to gold. The 1,3-diphenyl trioxadiborrin ligand of 1 has a larger absolute binding enthalpy to gold than its ß-diketonate analogue. Conjugation between boron and aryl substituents delocalizes charge and attenuates the trioxadiborrin's binding capacity. Steric effects that disrupt conjugation between boron and aryl substituents cause the trioxadiborrin to chelate more tightly. Fragment bond orders are divided into in-plane and out-of-plane contributions for square planar 1. In-plane bonding accounts for 88% of bond order between (tpy)Au2+ and the trioxadiborrin ligand. Cyclometalated gold(III) trioxadiborrin complexes were previously shown to be phosphorescent. Spin-unrestricted triplet-state geometry optimizations find that the ten largest excited-state distortions all occur on the tpy ligand. A plot of spin density in triplet 1 shows spin to reside predominantly on tpy. The 77 K luminescence spectrum of 1 is reported here. Time-dependent DFT and configuration interaction singles calculations (corrected for doubles excitations) overestimate the emission energy by ∼ 0.12 eV.