Kinetics of Fluorescence Quenching by Electron and H‐Atom Transfer

Abstract Fluorescence quenching rate constants, k q , ranging from 10 6 to 2 × 10 10 M −1 sec −1 , of more than 60 typical electron donor‐acceptor systems have been measured in de‐oxygenated acetonitrile and are shown to be correlated with the free enthalpy change, Δ G 23 , involved in the actual electron transfer process magnified image in the encounter complex and varying between + 5 and −60 kcal/mole. The correlation which is based on the mechanism of adiabatic outer‐sphere electron transfer requires Δ G ≠ 23 , the activation free enthalpy of this process to be a monotonous function of Δ G 23 and allows the calculation of rate constants of electron transfer quenching from spectroscopic and electrochemical data. A detailed study of some systems where the calculated quenching constants differ from the experimental ones by several orders of magnitude revealed that the quenching mechanism operative in these cases was hydrogen‐atom rather than electron transfer. The conditions under which these different mechanisms apply and their consequences are discussed.