Catalytic Properties of Luminescent Tris-Homoleptic Cyclometalated Iridium(III) Complexes in the Oxidation of Morin in Visible Light

Abstract

The photo-oxidation of Morin, 2′,3,4′,5,7-pentahydroxyflavone by six luminescent homoleptic tris-cyclometalated iridium(III) complexes was investigated with the aim of evaluating the catalytic properties of the complexes. The Iridium complexes were synthesized using 2-(1-naphthyl)-pyridine (npy) ligand and its derivatives such as npy-OMe, npy-CF3 and npy-Me to form Tris-homoleptic cyclometalated complexes; Ir(npy)3, Ir(npy-OMe)3, Ir(npy-CF3)3, Ir(npy-Me)3, Ir(Me-npy-Me)3, and Ir(Me-npy)3 with substitution at para position relative to nitrogen. The ligand substitution positions were found to influence the excited state lifetimes, where the complexes exhibited long lifetimes, τ, 1.4 – 3.6 μs, ensuring time for substrates to react before relaxation to ground state. All the six complexes displayed reversible or pseudo reversible redox processes with ground state oxidation potential range of 0.57 to 0.93V compared to Standard Calomel Electrode in CH2Cl2. The complexes degraded morin with rate constants kobs between 0.023-0.036 s -1 within a timescale of 12 minutes. The Ir(npy-Me)3 complex was found to have a high degradation with a rate constant of kobs = 0.036 s -1. Degradation reactions using all the six Iridium (III) complexes photoredox catalysts were found to follow first order kinetics and ca. 10-fold faster compared to similar oxidative reactions.