Excited-state electron-transfer quenching by a series of water photoreduction mediators

Rate constants k_q for the quenching of the excited state of Ru(bipy)₃²⁺ by a series of viologen salts having different redox potential E_{$\text{1}\text{2}$} have been determined in deaerated aqueous solutions at pH = 5 by laser flash photolysis. The k_q values are found to decrease with increasing —E_{$\text{1}\text{2}$} and to correlate with the reaction free-energy change ΔG. Such a correlation is shown to be consistent with the Rehm—Weller model for electron-transfer reactions.