Preparation and Spectroscopic and Spectroelectrochemical Characterization of Copolymers of 3-Alkylthiophenes and Thiophene Functionalized with an Azo Chromophore

Małgorzata Zagórska , Irena Kulszewicz-Bajer , Adam Proń , J. Sukiennik , P. Raimond , F. Kajzar , A.-J. Attias , M. Łapkowski

Abstract

New polythiophene derivatives containing a nonlinear optical chromophore were prepared via copolymerization of 3-alkylthiophene and 2-[N-ethyl-N-[4-[(4-nitrophenyl)azo]phenyl]amino]ethyl 3-thienylacetate. The presence of chromophore groups in the copolymer chain was confirmed by 1H NMR, 13C NMR, and FTIR spectroscopies as well as by elemental analysis. The introduction of azo dye as a side group to the conjugated polythiophene backbone significantly alters electrochemical and spectroelectrochemical behavior of these compounds as compared to poly(3-alkylthiophene) homopolymers. In particular, two redox processes are observed by cyclic voltammetry. The first anodic peak at lower potentials corresponds to the oxidative doping of the polymer whereas the second one is associated with the oxidation of the chromophore side group to a radical cation. Electrochemical oxidation of the copolymers results in a gradual bleaching of the absorption peak ascribed to the π?π* transition in the polyconjugated system. At the same time the absorption peak characteristic of the chromophore undergoes a bathochromic shift from 485 to 516 nm. Thus, in the spectra of the oxidatively doped copolymers an additional peak unobserved in poly(3-alkylthiophene) homopolymers is present in addition to the doping-induced absorption in the near-infrared part at the spectrum. This additional peak has an important influence on the Raman spectroelectrochemical behavior of the prepared copolymers as probed by the green (?max = 514 nm) excitation line. Electrochemical oxidation significantly worsens the resonance conditions for the vibrations of the conjugated backbone whereas it improves the resonance conditions for the vibrations associated with the chromophore side groups. As a result at lower potentials only the lines characteristic of the 2,5-disubstituted thienylene ring are registered, and at higher potentials, lines due to the chromophore dominate the spectrum.
Author Małgorzata Zagórska KChTP
Małgorzata Zagórska,,
- Chair Of Polymer Chemistry And Technology
, Irena Kulszewicz-Bajer KChTP
Irena Kulszewicz-Bajer,,
- Chair Of Polymer Chemistry And Technology
, Adam Proń KChTP
Adam Proń,,
- Chair Of Polymer Chemistry And Technology
, J. Sukiennik
J. Sukiennik,,
-
, P. Raimond
P. Raimond,,
-
, F. Kajzar
F. Kajzar,,
-
, A.-J. Attias
A.-J. Attias,,
-
, M. Łapkowski
M. Łapkowski,,
-
Journal seriesMacromolecules, ISSN 0024-9297
Issue year1998
Vol31
No26
Pages9146-9153
DOIDOI:10.1021/ma9806561
URL http://dx.doi.org/10.1021/ma9806561
Score (nominal)45
Publication indicators WoS Impact Factor: 2006 = 4.277 (2) - 2007=4.533 (5)
Citation count*54 (2018-06-17)
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