CHEMILUMINESCENCE FROM THE REDUCTION OF AROMATIC AMINE CATIONS AND RUTHENIUM(III) CHELATES*,‡

Abstract— –Chemiluminescence is reported from two types of reactions; those involving the reduction of amine cations yield fluorescence amines: RN H₂^+m+ reductant → RN H₂+hv and those involving reduction of transition metal chelates where the reduced form of the chelate is fluorescent: ML_x⁺⁽ⁿ⁺¹⁾+ reductant →ML_x⁺ⁿ+hv The results reported here are for reduction of the cation radical of 1,6-diaminopyrene and ruthenium (III) chelates where chelate ligands are substituted 1,10-phenanthrolines or 2,2'-bipyridine. Reducing agents for 1,6-diaminopyrene were hydrazine or the naphthalene radical anion; for the ruthenium chelates either hydroxyl ion or hydrazine in acid solution. A detailed study is reported for the kinetics of the ruthenium (III)-hydrazine reaction, using a computer kinetic modeling program. A quantitative fit of the experimental data to computer-generated curves can be accomplished at low hydrazine concentrations. At higher hydrazine concentrations the correct qualitative shapes of curves can be generated but the quantitative fit is not exact.