In this review article, we give a general introduction on the mechanisms involved in organic chemiluminescence, where three basic models for excited state formation are presented. The chemiluminescence properties of 1,2-dioxetanes - four membered ring peroxides - are briefly outlined in the second part. In the main part, the mechanisms involved in the decomposition of 1,2-dioxetanes and analogous peroxides are discussed: (i) the unimolecular decomposition of 1,2-dioxetanes; (ii) the electron transfer catalyzed decomposition of peroxides by an intermolecular CIEEL (Chemically Initiated Electron Exchange Luminescence) mechanism; (iii) 1,2-dioxetane decomposition catalyzed by an intramolecular electron transfer mechanism (intramolecular CIEEL). Special emphasis is given to the latter subject, where recent examples with potential analytical applications are presented.
1,2-dioxetanes; peroxide decomposition; chemiluminescence; CIEEL (Chemically Initiated Electron Exchange Luminescence)
