A1 Vertaisarvioitu alkuperäisartikkeli tieteellisessä lehdessä
pi-dimer of an aniline dimer: An ESR-UV-Vis spectroelectrochemical study
Tekijät: Petr A, Wei D, Kvarnstrom C, Ivaska A, Dunsch L
Kustantaja: AMER CHEMICAL SOC
Julkaisuvuosi: 2007
Lehti:Journal of Physical Chemistry B
Tietokannassa oleva lehden nimiJOURNAL OF PHYSICAL CHEMISTRY B
Lehden akronyymi: J PHYS CHEM B
Vuosikerta: 111
Numero: 43
Aloitussivu: 12395
Lopetussivu: 12398
Sivujen määrä: 4
ISSN: 1520-6106
DOI: https://doi.org/10.1021/jp073612f
Tiivistelmä
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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