UV/Vis/NIR spectral properties of triarylamines and their corresponding radical cations
2005
Abstract The one-electron oxidation potential of 10 triarylamines 1 – 10 with all permutations of chloro-, methoxy- and methyl-substituents in the three para -positions were determined by cyclic voltammetry. The half wave potential E 1/2 (I) of the first oxidation wave correlates linearly with the number of chloro- and methoxy-substituents. A high long-term stability of the first oxidation wave for all triarylamines was observed by multi-cycle thin-layer measurements. AM1-CISD derived values of the absorption energies are in good agreement with the experiments but differ strongly for the oscillator strengths as well as for neutral compounds 1 – 10 and their corresponding mono radical cations. The small solvent dependence of the experimental UV/Vis spectra in CH 2 Cl 2 and MeCN reflects a minor charge transfer (CT) character of the electronic transitions of neutral and cationic compounds.
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