Dual Luminescence, Interligand Decay, and Nonradiative Electronic Relaxation of Cyclometalated Iridium Complexes in Solution

Femtosecond broadband photoluminescence studies are presented for Ir(ppy)3 (Ir1), Ir(ppy)2(pic) (Ir2), Ir(ppy)2(bpy)(PF6) (Ir3), Ir(ppz)3 (Ir4), and Ir(ppz)2dipy (Ir5) (where ppy = 2-phenylpyridine, pic = picolinate, bpy = 2,2′-bipyridine, ppz = 1-phenylpyrazole, and dipy = 5-phenyldipyrrinato) in solution. Upon 400-nm excitation of Ir1–Ir3, we observed a prompt population of the lowest MLCT states. The higher states decay on an ultrafast time scale (3MLCT state undergoes further vibrational relaxation on a 1-ps time scale. In Ir3, this relaxation is accompanied by an interligand decay from the ppy to the bpy ligand in ∼1.5 ps. For the ppy-containing complexes (Ir1 and Ir2), we found that, …