Luminescence quenching of Ru(II)-diimine complexes with Cr(VI) ions: Steady-state and time-resolved studies

Abstract

Luminescence quenching of [Ru(bpy)(CN)4]2−, [Ru(phen)(CN)4]2−, [Ru(bpy)3]2+ and [Ru(phen)3]2+ by hexavalent chromium ion in aqueous media were investigated by steady-state and time-resolved measurements. Effect of pH on the luminescence quenching process is also investigated. It has been found that luminescence changes due to the interaction of all Ru(II) complexes with Cr(VI) ions were high at pH values less than or equal to 5.0 and negligible at pH ≥ 8.0. The experimental data of the quenching process were analyzed using Stern–Volmer (S–V) equations. The steady state luminescence emission data shows an upward curvature, indicating that the quenching is preceded by both dynamic and static quenching. For all studied complexes, the lifetime of the excited 3MLCT state decreases with increasing Cr(VI) concentration implying that the diffusion is mainly responsible for the quenching process. The Stern–Volmer dynamic quenching constants (KD) and the bimolecular quenching rate constant for the quenching process (kq) were calculated by applying the Stern–Volmer equation to the luminescence decay data. The bimolecular quenching rate constants (Kq) were found to increase in the order [Ru(bpy)(CN)4]2− < [Ru(phen)(CN)4]2− < [Ru(phen)3]2+ < [Ru(bpy)3]2+ which correlates will with the oxidation potentials of Ru(II) complexes. The association constants for Ru(II)-Cr(VI) system were calculated using the Benesi-Hildebrand equation and found to be 3.0 × 103, 2.5 × 103, 1.2 × 103, 7.1 × 103 M−1 for [Ru(bpy)(CN)4]2−, [Ru(phen)(CN)4]2−, [Ru(bpy)3]2+ and [Ru(phen)3]2+ respectively, which is interpreted in terms of the dynamic (diffusion) and the sphere of action (static) quenching models.