Ultrafast luminescence in Ir(ppy)₃

A femtosecond luminescence and transient absorption study of fac-tris(2-phenylpyridine) iridium(III) [Ir(ppy)₃] is reported. An emission with a lifetime component of 230 fs in the spectral region 500–560 nm is assigned to the population equilibration between electronic substates of the lowest excited triplet state, with energy dissipation by intramolecular vibrational redistribution. At shorter wavelengths a strong emission with a faster decay was observed and is attributed to a state with a higher admixture of singlet character. A slower decay on a 3 ps time scale is attributed to vibrational cooling. The results contribute to an understanding of the photophysics of transition metal complexes.