A1 Refereed original research article in a scientific journal
pi-dimer of an aniline dimer: An ESR-UV-Vis spectroelectrochemical study
Authors: Petr A, Wei D, Kvarnstrom C, Ivaska A, Dunsch L
Publisher: AMER CHEMICAL SOC
Publication year: 2007
Journal:Journal of Physical Chemistry B
Journal name in sourceJOURNAL OF PHYSICAL CHEMISTRY B
Journal acronym: J PHYS CHEM B
Volume: 111
Issue: 43
First page : 12395
Last page: 12398
Number of pages: 4
ISSN: 1520-6106
DOI: https://doi.org/10.1021/jp073612f
Abstract
It is shown for the first time that the most important intermediate formed during aniline polymerization, the p-aminodiphenylamine, forms a pi-dimer under oxidation at room temperature in acidified organic solvents that are used in electropolymerization. N-Phenylquinonediimine, which is generally assumed to be formed under oxidation, is only formed in basic solutions and in ionic liquids. Most of the mechanistic studies reported so far take the formation of N-phenylquinonediimine under consideration, although it is not consistent with the UV-vis spectra measured during oxidation of p-aminodiphenylamine. The formation of a pi-dimer is very well consistent with the electronic spectra of the oxidation product. In this way the pi-dimer is very important for the, interpretation of the UV-vis spectra of higher oligomers and polyaniline as well. Furthermore, it offers a new interpretation of the redox behavior of p-aminodiphenylamine as found by cyclic voltarnmetry and has to be considered in the mechanism of the electrochemical polyaniline formation.
It is shown for the first time that the most important intermediate formed during aniline polymerization, the p-aminodiphenylamine, forms a pi-dimer under oxidation at room temperature in acidified organic solvents that are used in electropolymerization. N-Phenylquinonediimine, which is generally assumed to be formed under oxidation, is only formed in basic solutions and in ionic liquids. Most of the mechanistic studies reported so far take the formation of N-phenylquinonediimine under consideration, although it is not consistent with the UV-vis spectra measured during oxidation of p-aminodiphenylamine. The formation of a pi-dimer is very well consistent with the electronic spectra of the oxidation product. In this way the pi-dimer is very important for the, interpretation of the UV-vis spectra of higher oligomers and polyaniline as well. Furthermore, it offers a new interpretation of the redox behavior of p-aminodiphenylamine as found by cyclic voltarnmetry and has to be considered in the mechanism of the electrochemical polyaniline formation.
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