Abstract
The stabilization of Ru(bpy) 3 3+ from Ru(bpy) 3 2+ at room temperature by radiolysis of acidic concentrated alkali-metal halide aqueous solutions has been achieved. Stabilization at room temperature is of particular interest for potential light-energy storage systems. The yield of Ru(bpy) 3 3+ , as well as its half-life, depend strongly on the alkali-metal halide and acid concentrations. The Ru(bpy) 3 3+ yield increases with increasing LiCl concentration and attains a maximum value around 5–10 mM H + ; the yield decreases at both higher and lower pH. The stabilization of Ru(bpy) 3 3+ is optimal at [LiCl] 4 M and 5 mM H + . The half-lives of Ru(bpy) 3 3+ are 20 h and 7 days at [LiCl] = 4 and 8 M, respectively, which are ca. 10 to 100 times longer than in a solution without LiCl. The stability of Ru(bpy) 3 3+ also depends on the alkali-metal cation. The half-lives of Ru(bpy) 3 3+ vary from 7 to 20 h in the order K, Na and Li at 5 mM H + and 4 M alkali-metal halide solution. This cation effect on the stabilization of Ru(bpy) 3 3+ is interpreted in terms of the free water concentration and dynamic hydration properties in alkali-metal halide solutions.
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