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: MLx+(n+1)+ reductant →MLx+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.