Green electrochemiluminescence from ortho-metalated tris(2-phenylpyridine)iridium(III)

The electrochemiluminescence (ECL) of Ir(ppy)3 (ppy = 2-phenylpyridine) is reported in acetonitrile (CH3CN), mixed CH3CN/H20 (50:50 v/v), and aqueous (0.1 M KH2PO4) solutions with tri-n-propylamine as an oxidative-reductive coreactant. ECL efficiencies (phi(ecl), photons emitted per redox event) of 0.00092 in aqueous, 0.0044 in mixed, and 0.33 in CH3CN solutions for Ir(ppy)3 were obtained using Ru(bpy)3(2+) (bpy = 2,2'-bipyridine) as a relative standard (phi(ecl) = 1). Photoluminescence (PL) efficiencies of 0.039, 0.050, and 0.069 were obtained in aqueous, mixed, and acetonitrile solutions, respectively, compared to Ru(bpy)3(2+) (phi(em) = 0.042). The ECL spectra were identical to photoluminescence spectra (lambda(max) approximately equal to 517 nm), indicating formation of the same metal-to-ligand (MLCT) excited states in both ECL and PL. The ECL is linear over several orders of magnitude in mixed and acetonitrile solution with theoretical detection limits (blank plus three times the standard deviation of the noise) of 1.23 nM in CH3CN and 0.23 microM in CH3CN/ H20 (50:50 v/v).