Influence of Electrochemical Polymerization Temperature on the Chiroptical Properties of (+)-Camphorsulfonic Acid-Doped Polyaniline

The chiroptical properties of electrochemically deposited emeraldine salt PAn·(+)-HCSA (HCSA = 10-camphorsulfonic acid) films have been found to vary markedly with the temperature employed during polymerization. The circular dichroism spectra of such films grown at >40 °C are inverted compared to...

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Bibliographic Details
Published in:Macromolecules 2006-08, Vol.39 (17), p.5604-5610
Main Authors: Pornputtkul, Yingpit, Kane-Maguire, Leon A. P, Wallace, Gordon G
Format: Article
Language:English
Subjects:
Applied sciences
Exact sciences and technology
Physicochemistry of polymers
Polymerization
Polymers and radiations
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Summary:The chiroptical properties of electrochemically deposited emeraldine salt PAn·(+)-HCSA (HCSA = 10-camphorsulfonic acid) films have been found to vary markedly with the temperature employed during polymerization. The circular dichroism spectra of such films grown at >40 °C are inverted compared to the spectra of analogous films deposited at temperatures ≤25 °C, indicating an inversion of conformation for the polyaniline chains. These observations are rationalized in terms of a temperature-induced interconversion between the two diastereomeric emeraldine salt products from the doping of the growing polyaniline chains by the chiral (+)-CSA- anion. The marked temperature dependence of the diastereoselectivity highlights the importance of employing a fixed temperature during the electrosynthesis of optically active polyanilines.
ISSN:0024-9297
1520-5835
DOI:10.1021/ma052201z