Abstract

Abstract Three types of N,N,N′,N′-tetraaryl-1,3-phenylenediamines with bromo atoms as protecting groups were designed and synthesized. Electrochemical and novel electron transfer stopped-flow (ETSF) methods were invoked for characterizing the absorption spectra of the corresponding short-lived mono- and dicationic states. Useful molecular design rules for stabilizing the dicationic states of N,N,N′,N′-tetraaryl-1,3-phenylenediamines as precursors for positively charged high-spin systems were elucidated. An extended system, 3,3′-bis(diphenylamino)triphenylamine in the tricationic state with four bromo groups was also examined, being confirmed to give a ground-state triplet dication by ESR spectroscopy.

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