Theoretical Design of Blue-Color Phosphorescent Complexes for Organic Light-Emitting Diodes: Emission Intensities and Nonradiative Transition Rate Constants in Ir(ppy)2(acac) Derivatives

Theoretical calculations of phosphorescent spectra and nonradiative transition (NRT) rate constants for S1 -Aa T1, T1 -Aa S0, and S1 -Aa S0 were carried out to determine the best candidate for a blue-color phosphorescent complex among several derivatives of bis(2-phenylpyridine)(acetylacetonate)iridium(III). The geometries of the ground state (S0), the lowest triplet state (T1), and the lowest excited singlet state (S1) were optimized at the levels of density functional theory, in which B3LYP functionals and SBKJC+p basis sets were used. The NRT rate constants were derived by using a generating function method within the displaced harmonic oscillator model. The results of the calculation for phosphorescence showed that the introduction of F and/or CN substituents at the 4 '/6 '-th and 5 '-th sites in 2-phenylpyridinate (ppy) ligands, respectively, causes a blue shift of the emission spectra. They also suggest that Ir(5CN,6-F-ppy)2(acac), denoted 3(56) in the text, is a good candidate for a blue-color phosphorescent complex because a blue shift of emission spectra and a moderate intensity are obtained for phosphorescence and, furthermore, this complex is calculated to have a large rate constant for S1 -Aa T1 and relatively smaller rate constants for T1 -Aa S0 and S1 -Aa S0 based on the calculations of spin-orbit coupling and nonadiabatic coupling constants.