Back electron transfer in electron-exchange chemiluminescence of oxyaryl-substituted spiroadamantyl dioxetane, an analog of firefly bioluminescence

The viscosity dependence of the excitation yield of the singlet oxybenzoate anion, an emitter of electron-exchange chemiluminescence of oxyaryl-substituted spiroadamantyl dioxetane, a chemical analog of firefly bioluminescence, was studied. At 299, K the excitation yield increases from 8 to 23% as the content of diphenylmethane in its mixture with benzene increases to 97%. This effect was quantitatively interpreted in terms of a probabilistic model of the solvent-cage effect, assuming that the chemiexcitation results from the back electron transfer between the products of chemically initiated decomposition of the starting reagent. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 655–661, April, 2000.