A single starting component electrochemiluminescence system from which red, green, blue or white emission can be obtained, depending on the applied potential or the mode of the ECL experiment, is described. The convoluted ECL spectral responses observed at different potentials are readily explained using a 3D-ECL technique, where the ECL spectral profile is continuously monitored as a function of potential during voltammetric scanning. The 3D plots obtained using this technique implicate cross-annihilation ECL reactions involving the complex itself and stable products resulting from its electrolysis. Combining this information with knowledge of the energetic requirements of the various reactions involved, suggests a mechanism involving traces of two emissive products, related to the loss of a methyl group from the triazole moiety. These products, while barely detectable electrochemically, are sufficiently emissive to influence and even dominate the ECL emission under some conditions.