Phosphorescence studies of a series of facial homoleptic cyclometalated iridium(III) complexes have been carried out. The complexes studied have the general structure Ir(III)(C-N)(3), where (C-N) is a monoanionic cyclometalating ligand: 2-(5-methylthiophen-2-yl)pyridinato, 2-(thiophen-2-yl)-5-trifluoromethylpyridinato, 2,5-di(thiophen-2-yl)pyridinato, 2,5-di(5-methylthiophen-2-yl)pyridinato, 2-(benzo[b]thiophen-2-yl)pyridinato, 2-(9,9-dimethyl-9H-fluoren-2-yl)pyridinato, 1-phenylisoquinolinato, 1-(thiophen-2-yl)isoquinolinato, or 1-(9,9-dimethyl-9H-fluoren-2-yl)isoquinolinato. Luminescence properties of all the complexes at 298 K in toluene are as follows: quantum yields of phosphorescence Phi(p) = 0.08-0.29, emission peaks lambda(max) = 558-652 nm, and emission lifetimes tau = 0.74-4.7 micros. Bathochromic shifts of the Ir(thpy)(3) family [the complexes with 2-(thiophen-2-yl)pyridine derivatives] are observed by introducing appropriate substituents, e.g., methyl, trifluoromethyl, or thiophen-2-yl. However, Phi(p) of the red emissive complexes (lambda(max) > 600 nm) becomes small, caused by a significant decrease of the radiative rate constant, k(r). In contrast, the complexes with the 1-arylisoquinoline ligands are found to have marked red shifts of lambda(max) and very high Phi(p) (0.19-0.26). These complexes are found to possess dominantly (3)MLCT (metal-to-ligand charge transfer) excited states and have k(r) values approximately 1 order of magnitude larger than those of the Ir(thpy)(3) family. An organic light-emitting diode (OLED) device that uses Ir(1-phenylisoquinolinato)(3) as a phosphorescent dopant produces very high efficiency (external quantum efficiency eta(ex) = 10.3% and power efficiency 8.0 lm/W at 100 cd/m(2)) and pure-red emission with 1931 CIE (Commission Internationale de L'Eclairage) chromaticity coordinates (x = 0.68, y = 0.32).

A series of highly emissive three-coordinate copper(I) complexes, (dtpb)Cu(I)X [X = Cl (1), Br (2), I (3); dtpb =1,2-bis(o-ditolylphosphino)benzene], were synthesized and investigated in prototype organic light-emitting diodes (OLEDs). 1-3 showed excellent photoluminescent performance in both degassed dichloromethane solutions [quantum yield (Φ) = 0.43-0.60; lifetime (τ) = 4.9-6.5 μs] and amorphous films (Φ = 0.57-0.71; τ = 3.2-6.1 μs). Conventional OLEDs containing 2 in the emitting layer exhibited bright green luminescence with a current efficiency of 65.3 cd/A and a maximum external quantum efficiency of 21.3%.

A series of heteroleptic coinage metal(I) complexes [Cu(PP)(PS)] 1, [Ag(PP)(PS)] 2, and [Au(PP)(PS)] 3 [PP ¼ 1,2-bis(diphenylphosphino)benzene and PS À ¼ 2-diphenylphosphinobenzenethiolate] were synthesized.X-ray crystallography demonstrated that 1-3 possessed tetrahedral structures containing two types of bidentate ligands, PP and PS À . Photophysical studies and time-dependent density functional theory calculations indicated that the emission from 1-3 in the solid state at room temperature originated from thermally activated delayed fluorescence (TADF). The thiolate ligand with strong electron-donating character (PS À ) reduced the contribution from metal orbitals to the highest occupied molecular orbitals of the complexes, decreasing the metal-to-ligand charge-transfer character of the excited states of 1-3.The origin of TADF in 1-3 was attributed to ligand-to-ligand charge-transfer on the basis of molecular orbital calculations. Au(I) complex 3 was unstable in solution because of a rapid ligand exchange reaction, and Ag(I) complex 2 showed limited solubility in organic solvents. Cu(I) complex 1, which exhibited efficient green TADF with a maximum emission wavelength of 521 nm and a quantum yield of 0.52 in the solid state, was used to fabricate TADF-type organic light-emitting diodes via a wet process.