Stabilization and EPR characterization of Ru(bpy)33+ formed by radiolysis in concentrated alkali-metal halide solutions
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] ![[gt-or-equal]](https://www.rsc.org/images/entities/char_2a7e.gif)
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.
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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