Abstract
Electrogenerated chemiluminescence (ECL) has been observed during the reduction of peroxydisulfate (S 2O 8 2−) by electrogenerated radical anions of several aromatic compounds (Ar −) in 2:1 CH 3CN-benzene solutions. The ECL spectra that arise at the Ar reduction wave agree with the fluorescence spectra of the corresponding aromatic compound. The cyclic voltammetric Ar reduction waves in the presence of S 2O 8 2− were generally of the catalytic type, with Ar regenerated by the following chemical reaction with peroxydisulfate. Formation of Ar ★ with the resulting ECL was primarily caused by the Ar −/Ar + reaction, with Ar + generated via oxidation of Ar by SO 4 − (a product of the reduction of S 2O 8 2−). The relative ECL efficiencies qualitatively depend upon the stability of the hydrocarbon radical cations, with rubrene producing the most intense ECL. A tertiary reactant system in which thianthrene fluorescence was observed during the catalyzed reduction of S 2O 8 2− by the radical anion 2,5-diphenyl-1,3,4-oxadizole was also studied.
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