In Situ Spectroelectrochemical Investigations of Ru^II Complexes with Bispyrazolyl Methane Triarylamine Ligands

The synthesis and characterization of two triarylamine ligands, 4-(di(1H-pyrazol-1-yl)methyl)-N-(4-(di(1H-pyrazol-1-yl)methyl)phenyl)-N-phenylaniline (TPA-2bpm) and tris(4-(di(1H-pyrazol-1-yl)methyl)phenyl)amine (TPA-3bpm), containing the bispyrazolylmethane moiety and its RuII terpyridine complexes are presented. The redox properties of the ligands and RuII complexes are explored in detail through cyclic and square-wave voltammetry in addition to in situ UV-vis-near infrared, electron paramagnetic resonance, and fluorescence spectroelectrochemistry. It was demonstrated that the triarylamine radical cation was able to be generated, and further, TPA-2bpm underwent an electrochemically induced dimerization process.