EXCIPLEX STUDIES–V. ELECTRON EJECTION FROM INDOLE AND METHYL‐INDOLE DERIVATIVES*

Abstract

Abstract— Electron‐scavenging experiments with N 2 O as scavenger demonstrate at least two electron‐producing reactions of the excited singlet states of the exciplex species formed by indole or 1 ‐methyl‐indole with water. Most electrons reacting with N 2 O result from collision of the scavenger with a metastable state formed from the initial exciplex state but finite electron yields from indole and 1‐methyl‐indole at limiting scavenger concentrations suggest that the intermediate states also eject electrons directly into the solvent. The formation of the first metastable state from the fluorescent exciplex state has an activation energy, E M , estimated to be about 13 kcal/mole for both indole and 1 ‐methyl‐indole water exciplexes. The E M values for 1‐methyl‐indole from fluorescence and electron yields are the same, Indicating that at neutral and alkaline pH fluorescence quenching and electron extraction are both being controlled by the formation of the first metastable intermediate. Observed electron yields from indole‐water and indole‐methanol exciplexes are less than predicted using fluorescence data, although E M values of 1 kcal/mole are obtained for the indole‐methanol exciplex by both methods. At pH 12·0 and 28°C the total electron yields for indole‐water and 1 ‐methyl‐indole‐water exciplexes are 0·30 and 0·25, respectively. The residual yields attributed to outright formation of hydrated electrons from the initial exciplex excited stateare 0·11 and 0·05, respectively. Electron yields from the indole‐water exciplex are strongly pH dependent only near pH 1 where the fluorescence yields as well as the electron yields decrease rapidly with increasing acidity. The 1‐methyl‐indole‐water exciplex shows an additional pH dependence which is first‐order in hydrogen‐ion activity and has an effective p K a of about 11·5. Comparable yields for indole and 1‐methyl‐indole are found only above pH 12. High electron yields are found with indole in the exciplex‐forming solvent dioxane and in the non‐exciplex forming solvent cyclohexane. For the latter system electrons are probably derived only from the lowest excited state of indole on collision with N 2 O.