ENERGETICS AND KINETICS OF HOMOGENEOUS ELECTROCHEMILUMINESCENT ELECTRON-TRANSFER REACTIONS IN NAPHTHALIMIDE SOLUTIONS

Free activation energies and rate constants for bimolecular reactions of electron transfer (RET) between electrogenerated radical ions A(-.) and A(+.) of electrochemiluminophores A (substituted naphthalimides) are calculated. A correlation analysis is conducted for the first time , yielding mechanisms and kinetics of RET that occur in an anomalous ( in terms of formation of nonexcited products) region of electron trans itions. The correlation dependences of the electrochemiluminescence (E CL) intensity on the free activation energy of RET are plotted. The co rrelation coefficients pertaining to each series of naphthalimide comp ounds under study are found for different electrolysis conditions. Com paring the above dependences and coefficients shows adequacy of the ex pressions proposed for the calculation of rate constants inherent in h omogeneous RET. The calculations are made in the framework of the know n theories, describing intermolecular exothermic electron transitions, which most closely coincide with the experimental dependences of the ECL intensity on the free activation energy.