DYNAMIC QUENCHING OF RU(BPY)32+ EMISSION IN THE POTENTIAL-FIELD OF A POLYELECTROLYTE

The effect of PVS on the quenching of Ru(bpy)32+* by positive cations is shown here to be primarily a dynamic quenching. The reaction was shown to occur mainly in the reduced volume of the polymer field in which both the chromophore and the quencher reside. Since the rate constant calculated for the reaction in that reduced volume closely resembles that in a bulk reaction, it was inferred that no change in the mechanism occurs when the reaction takes place in the potential field of the polyelectrolyte; i.e., the reaction most probably is an electron-transfer reaction. In the case of quenching by Fe(III), cross-linking by the iron ions is the preferred explanation for the dependence of the rate constant on [Fe(III)]. © 1979 American Chemical Society.