Carbonyl group, excited Dioxetane

The optically active 1,2-dioxetane of 2,4-adamantanedione (89) was synthesized. Thermal activation of 89 yielded chemiluminescence (Xmax = 420 nm characteristic of ketone fluorescence), pointing to intermediate 90 which is chiral only in its excited state due to the out-of-plane geometry of one of the two carbonyl groups. However, circular polarization of chemiluminescence measurement of 90 has not detected optical activity at the moment of emission. The authors have concluded that fast, relative to the lifetime of ketone singlet excited state, intramolecular n, it energy transfer caused racemization of 90196. 

Another class of radical is considered at some length elsewhere in this book. The chemiluminescent decomposition of alkyl peroxides occurs by a variety of routes, but the invariable formation of a carbonyl group in an excited state removes much of the difficulty attending the examples discussed immediately above. There are some well understood cases such as the dioxetans and a range of more obscure ones such as those involved in luminescence attending phagocytosis and polymer degradation. 

The 1,2-dioxetanes are another important group of chemiluminescent compounds. These compounds are oxidatively cleaved thermally in a concerted fashion to yield two carbonyl moieties, one of which is excited. The mechanism of this cleavage has been described as a chemically initiated electron-exchange... 

Fig. 32. Possible mechanisms for the thermal decomposition of dioxetanes [adapted from Hummelen et al. (H21), with permission). In (a), a concerted bond cleavage leads directly to two carbonyl products, one of which is in the excited state and emits light (M15, M16). The substituents R1-R4 can be simple alkyl or alicyclic groups. In (b), homolytic bond cleavage leads to a biradical that exists as an equilibrium mixture of singlet-state (f ) and triplet-state (t t) forms. As before, chemiluminescence emission probably occurs via the excited singlet-state carbonyl product arising from the homolytic bond cleavage of the intermediate biradical (R5, R6). The substituents R and Ar can include uncharged alkyl, alicyclic, and aromatic groups.

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