1.2- Dioxetanes catalyzed decomposition

Nevertheless, there are two highly efficient CL systems which are believed to involve the CIEEL mechanism in the chemiexcitation step, i.e. the peroxyoxalate reaction and the electron transfer initiated decomposition of properly substituted 1,2-dioxetanes (Table 1)17,26 We have recently confirmed the high quantum yields of the peroxyoxalate system and obtained experimental evidence for the validity of the CIEEL hypothesis as the excitation mechanism in this reaction. The catalyzed decomposition of protected phenoxyl-substituted 1,2-dioxetanes is believed to be initiated by an intramolecular electron transfer, analogously to the intermolecular CIEEL mechanism. Therefore, these two highly efficient systems demonstrate the feasibility of efficient excited-state formation by subsequent electron transfer, chemical transformation (cleavage) and back-electron transfer steps, as proposed in the CIEEL hypothesis. 

Zaklika, K.A., Burns, P.A. and Schaap, A.P. (1978) Enhanced chemiluminescence from the silica gel catalyzed decomposition of a 1,2-dioxetane. Journal of the American Chemical Society, 100 (1), 318—320. 

While the unimolecular chemiluminescence of dioxetanones appears to fall easily within the framework of conventional dioxetane chemiluminescence, the chemiluminescence of dioxetanones in the presence of certain fluorescers falls resoundingly outside that framework. Adam et al. (1974) noted that the addition of rubrene to solutions of dimethyldioxetanone gave a yield of light twenty times that obtained when an equivalent concentration of 9,10-diphenylanthracene was added. Importantly, the apparent dissimilarity between rubrene and diphenylanthracene is inexplicable by any conventional mechanism of dioxetane decomposition. Also, significantly, Adam et al. (1974) observed an increase in the first-order decay constant of the dioxetanone with the addition of rubrene, an observation for which they did not offer an explanation. Sawaki and Ogata (1977) also observed an unusual dependence of the chemiluminescence yield on the identity of added fluorescer in the base-catalyzed decomposition of or-hydroperoxyesters, for which a dioxetanone intermediate was proposed (25). 

Like other peroxides, also dioxetanes are sensitive to the presence of metal ions and their complexes, which catalyze the decomposition of the dioxetane molecule. In most cases, this decomposition is dark, i.e. no chemiluminesce is generated in such a catalytic cleavage42. An informative exception, for instance, constitutes the chemiluminescent decomposition of the dioxetane 19 in Scheme 13, initiated by the ruthenium complex Ru(bipy)3Cl243. It has been shown that this chemiexcitation derives from the valence change of the ruthenium ion in the process Ru3+ I e — Ru2+, for which the efficiency of the excited-state generation may be as much as 40%44. Hence, when the radical anion of the carbonyl cleavage fragment from the dioxetane and the Ru3+ ion are formed in... 

On the basis of mechanistic studies, mainly on these isolable cyclic four-membered peroxides (1 and 2), two main efficient chemiexcitation mechanisms can be defined in organic peroxide decomposition (i) the unimolecular decomposition or rearrangement of high-energy compounds leading to the formation of excited-state products, exemplified here in the case of the thermal decomposition of 1,2-dioxetane (equation l)11-15-19 and (ii) the decomposition of a peroxide, catalyzed by the interaction with a second compound, which is ultimately formed in its electronically excited state. 

The reaction of divalent metals, such as copper, nickel, and so on, with dioxetanes in methanol leads to clean catalytic decomposition into carbonyl fragments/ The reaction rates increase with increasing Lewis acidity of the divalent metal and indicate, therefore, typical electrophilic cleavage of the dioxetane. On the other hand, univalent rhodium and iridium complexes catalyze the decomposition of dioxetanes into carbonyl fragments via oxidative addition. 

We have found that decomposition of adamantylidenadamantane-l,2-dioxetane (DO), catalyzed by Eu(FOD)3 proceeds through the formation of the complex between DO and the Eu(FOD)3. Apart from the expected chemiluminescence at K 613 nm ( Dq), emission from the Di excited level of the Eu(III) at X 535 nm has... 

An additional novel use of lanthanide shift reagents emerged from studies of metal-catalyzed light emission and decomposition of dioxetans (McCapra and Watmore, 1982). In the case of dioxetan, G (see fig. 4), the pseudo first-order... 

---