Abstract
Quenching of excited Ru(bpy)/sub 3//sup 2 +/ by methylviologen has been studied in a cellulose matrix by using both steady-state and pulsed laser photolysis techniques. The quenching was found to proceed via an adiabatic electron-transfer mechanism with a rate constant which depends exponentially on the reacting distance; k(r) = 1.0 x 10/sup 10/ exp(-0.46r) s/sup -1/. Due to Franck-Condon factors the back reaction is approximately 3 orders of magnitude slower. The cellulose medium acts as a reducing agent interfering with the back reaction which results in a long-lived steady-state yield of reduced methylviologen. This yield depends on the concentration of the reacting species and reaches a maximum value of 4.6% in the sample containing (Ru(bpy)/sub 3//sup 2 +/) = 0.01 mol dm/sup -3/ and (MV/sup 2 +/) = 0.04 mol dm/sup -3/. Other details of the reaction mechanism are also given. 21 references, 5 figures, 1 table.
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