Role of the Diphosphine Chelate in Emissive, Charge-Neutral Iridium(III) Complexes

A class of neutral tris-bidentate Ir^III metal complexes incorporating a diphosphine as a chelate is prepared and characterized here for the first time. Treatment of [Ir(dppBz)(tht)Cl₃ ] (1, dppBz=1,2-bis(diphenylphosphino)benzene, tht=tetrahydrothiophene) with fppzH (3-trifluoromethyl-5-(2'-pyridyl)-1H-pyrazole) afforded the dichloride complexes, trans-(Cl,Cl)[Ir(dppBz)(fppz)Cl₂ ] (2) and cis-(Cl,Cl)[Ir(dppBz)(fppz)Cl₂ ] (3). The reaction of 3 with the dianionic chelate precursor, 5,5'-di(trifluoromethyl)-3,3'-bipyrazole (bipzH₂ ) or 5,5'-(1-methylethylidene)-bis(3-trifluoromethyl-1H-pyrazole) (mepzH₂ ), in DMF gave the tris-bidentate complex [Ir(dppBz)(fppz)(bipz)] (4) or [Ir(dppBz)(fppz)(mepz)] (5), respectively. In contrast, a hydride complex [Ir(dppBz)(fppz)(bipzH)H] (6) was isolated instead of 4 in protic solvent, namely: diethylene glycol monomethyl ether (DGME). All complexes 2-6 are luminescent in powder form and thin films where the dichlorides (2, 3) emit with maxima at 590-627 nm (orange) and quantum yields (QYs) up to 90 % whereas the tris-bidentate (4, 5) and hydride (6) complexes emit at 455-458 nm (blue) with QYs up to 70 %. Hybrid (time-dependent) DFT calculations showed considerable metal-to-ligand charge transfer contribution to the orange-emitting 2 and 3 but substantial ligand-centered ³ π-π* transition character in the blue-emitting 4-6. The dppBz does not participate in the radiative transitions in 4-6, but it provides the rigidity and steric bulk needed to promote the luminescence by suppressing the self-quenching in the solid state. Fabrication of an organic light-emitting diode (OLED) with dopant 5 gave a deep-blue CIE chromaticity of (0.16, 0.15). Superior blue emitters, which are vital in OLED applications, may be found in other neutral Ir^III complexes containing phosphine chelates.