Diphenoyl peroxide, chemiluminescence

Figure 13 Chemiluminescent reaction of diphenoyl peroxide based on CIEEL mechanism.

Chemiluminescence. The mechanisms behind this phenomenon, as induced by the reaction of, e.g. diphenoyl peroxide and an easily oxidized fluorescent molecule has been brilliantly illuminated by Schuster and co-workers (Schuster, 1979b Koo and Schuster, 1978) who proposed the CIEEL pathway (Chemically Initiated Electron Exchange Luminescence) according to (12). Note that two electron-transfer steps are postulated, the... 

The chemiluminescent reaction of diphenoyl peroxide [26] with easily oxidized, aromatic hydrocarbons, reported by Koo and Schuster (1977b, 1978), was the first well-defined example of an electron-exchange chemiluminescent reaction of an organic peroxide. Its study led to the postulation of chemically initiated electron-exchange luminescence as a generalized mechanism for efficient chemical light formation (Schuster, 1979 Schuster et al., 1979). 

More recently, direct experimental verification of the existence of radical ions in the reaction of [261 with activators and of their intermediacy in the chemiluminescence process was obtained by applying nanosecond laser spectrophotometric techniques to the study of this reaction (Horn and Schuster, 1979). Excited singlet pyrene was generated by irradiation with a nitrogen laser. The fluorescence of pyrene was quenched by diphenoyl peroxide... 

Intramolecular anhydride/peranhydride exchange through in situ formation of a peroxy p-nitrophenyl anhydride intermediate has been inferred to form diphenoyl peroxide, as evidenced by its chemiluminescent decomposition (Scheme 21) <86JOC2050>. 

Catalan , L.H. and Wilson, T., Electron transfer and chemiluminescence. Two inefflcient systems l,4-dimethoxy-9,10-diphenylanthracece peroxide and diphenoyl peroxide,/. Am. Chem. Soc., Ill, 2633, 1989. 

The term CIEEL was coined by Schuster [3] in a re- appraisal of the chemiluminescence of diphenoyl peroxide [4] (14). 

Fig. 8. Chemiluminescence of Phthaloyl Peroxide (PPO) and Diphenoyl Peroxide (DPO) with 9,10- Bis(phenylethynyl)-anthracene (BPEA). Solvent Dimethylphthalate, Temp. 22°C, Nitrogen Atmosphere.

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