CYCLIC PEROXIDE .81. FLUORESCER-ENHANCED CHEMI-LUMINESCENCE OF ALPHA-PEROXYLACTONES VIA ELECTRON EXCHANGE

Fluorescence of polycyclic aromatic hydrocarbons such as rubrene (Ru), naphthacene (Naph), perylene (Per), and 9,10-diphenylanthracene (DPA) is chemienergized by the dimethyl α-peroxylactone. Two modes of chemienergization operate concurrently, namely, the classical energy transfer process, involving rate-determining unimolecular decomposition of the α-peroxylactone, and the more efficient (ca. 50-fold) novel electron exchange luminescence process, involving a rate-determining bimolecular reaction between the fluorescers and α-peroxylactone. In the latter case the fluorescers enhance the chemiluminescence by catalyzing the decomposition of the α-peroxylactone. The catalysis is in the order of the oxidation potentials of the fluorescers, i.e., Ru > Naph > Per > DPA, as evidenced by a linear dependence of the catalytic rate constants (kcat) and activation energies (Ea) on the fluorescer oxidation potentials (Eox). The β-peroxylactones are ineffective as electron exchange substrates. © 1979, American Chemical Society. All rights reserved.