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

摘要

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 excittion 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 inditiated decomposition of the starating reagent.