Journal
CHEMICAL PHYSICS
Volume 316, Issue 1-3, Pages 141-152Publisher
ELSEVIER SCIENCE BV
DOI: 10.1016/j.chemphys.2005.05.009
Keywords
cyclic voltammetry; radical cations; semiempirical calculations; triarylamines; UV/Vis spectroscopy
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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 CH2Cl2 and MeCN reflects a minor charge transfer (CT) character of the electronic transitions of neutral and cationic compounds. (C) 2005 Elsevier B.V. All rights reserved.
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