Electrogenerated chemiluminescence: Part XXVII. E.C.L. and electrochemical studies of selected laser dyes

The electrogenerated chemiluminescence (e.c.l.) and electrochemistry of the laser dyes, coumarin-2, coumarin-30, rhodamine-6G (perchlorate), rhodamine-B (perchlorate), oxazine-1 (perchlorate), and Nile Blue (perchlorate) were studied in acetonitrile using 0.1 M tetra-n-butylammonium perchlorate (TBAP) as a supporting electrolyte. Rather low intensity e.c.l. was obtained for all dyes except Nile Blue. A study of the electrochemical oxidation and reduction of coumarin-30, oxazine-1 and rhodamine-6G using cyclic voltammetry and controlled potential coulometry demonstrated that chemical side reactions of the electrogenerated reactants are responsible for the low e.c.l. efficiency. In several cases the one-electron transfer reaction at the electrode is followed by a dimerization reaction. The neutral free radical formed on reduction of oxazine-1 was investigated by electron spin resonance spectroscopy and coupling constants for it are reported. Some experiments in which the e.c.l. of mixtures of the dyes with rubrene or 9,10-diphenylanthracene were determined are also described.