Chemiluminescence intermolecular electron transfer

Although there are many components in a mechanistic description of a chemiluminescent reaction, the heart of the matter is the actual excitation step. Several such steps have been identified. Some are molecular in character e. g. the decomposition of dioxetans and some are intermolecular electron transfer steps. There is an intermediate class in which the step can be formulated as an /n ramolecular electron transfer. Many luminescent reactions have been ascribed to this category with varying degrees of confidence. Cyclic hydrazides such as luminol belong rather uncertainly here. Electron rich dioxetans and dioxetanones and the luciferins with such intermediates on the pathway are a little more reasonably assigned to an intramolecular electron transfer mechanism. Even here however caution is required in that direct evidence for discrete electron transfer will by its very nature be almost impossible to obtain and will probably remain circumstantial. 

The peroxyoxalate system is the only intermolecular chemiluminescent reaction presumably involving the (71EEL sequence (Scheme 44), which shows high singlet excitation yields (4>s), as confirmed independently by several authors Moreover, Stevani and coworkers reported a correlation between the singlet quantum yields, extrapolated to infinite activator concentrations (4> ), and the free energy involved in back electron-transfer (AG bet), as well as between the catalytic electron-transfer/deactivation rate constants ratio, ln( cAx( i3), and E j2° (see Section V). A linear correlation of ln( cAx( i3) and E /2° was obtained for the peroxyoxalate reaction with TCPO and H2O2 catalyzed by imidazole and for the imidazole-catalyzed reaction of 57, both in the presence of five activators commonly used in CIEEL studies (anthracene, DPA, PPO, perylene and rubrene). A further confirmation of the validity of the CIEEL mechanism in the excitation step of... 

Despite the clear implication of the involvement of intramolecular electron transfer in the chemiluminescence of certain dioxetanes, there have been no clear examples of intermolecular electron exchange luminescence processes with dioxetanes. In a recent note, however, Wilson (1979) reports the observation of catalysis of the chemiluminescence of tetramethoxy-1,2-dioxetane by rubrene and, most surprisingly, by 9,10-dicyanoanthracene. While catalysis by the added fluorescers was not kinetically discernible, a lowering of the activation energy for chemiluminescence was observed. These results were interpreted not in terms of an actual electron transfer with the formation of radical ions, but rather in terms of charge transfer interactions between fluorescer and dioxetane in the collision complex. In any event, these results certainly emphasize the need for caution in considering the fluorescer as a passive energy acceptor in dioxetane chemiluminescence. 

The main features of the chemiluminescence mechanism are exemplarily illustrated in Scheme 11 for the reaction of bis(2,4,6-trichlorophenyl)oxalate (TCPO) with hydrogen peroxide in the presence of imidazole (IMI-H) as base catalyst and the chemiluminescent activators (ACT) anthracene, 9,10-diphenylanthracene, 2,5-diphenyloxazole, perylene and rubrene. In this mechanism, the replacement of the phenolic substituents in TCPO by IMI-H constitutes the slow step, whereas the nucleophilic attack of hydrogen peroxide on the intermediary l,l -oxalyl diimidazole (ODI) is fast. This rate difference is manifested by a two-exponential behavior of the chemiluminescence kinetics. The observed dependence of the chemiexcitation yield on the electrochemical characteristics of the activator has been rationalized in terms of the intermolecular CIEEL mechanism (Scheme 12), in which the free-energy balance for the electron back-transfer (BET) determines whether the singlet-excited activator, the species responsible for the light emission, is formed ... 

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