A polyalkylated triamine, 2,2,4,4 '-tetrabromo-4 ''-methyl-5,5 '-bis(di(3,4-di-methylphenyl)amino)triphenylamine, was designed and successfully synthesized as a model precursor for purely organic cationic high-spin systems. Cyclic voltammetry measurement revealed that the triamine gives stable mono- and dicationic states and fairly unstable tricationic state. Novel electron transfer stopped-flow (ETSF) methods were invoked for characterizing the absorption spectra of the corresponding mono- and oligo-cationic states. The triplet state of the dication was confirmed by ESR spectroscopy. (c) 2006 Elsevier Ltd. All rights reserved.