Geometrical Changes in Conjugated Polyenes

Document Type

Article

Publication Date

1-1-1985

Abstract

The activation energy and the threshold temperature of isomerization are determined for the cis-trans conversion of polyacetylene (26.5 kJ/mol and 236 K) and poly( phenyl acetylene) (42.5 kJ/mol and 373 K) in the solid state. Based on the low activation energy of conversion, a mechanism is proposed for the isomerization of cis-rich polyacetylene, which involves the delocalization of electrons in the first step followed by formation of trans geometries through their relocalization in the cisoidal form and rotation around single bonds to form stable transoidal sequences. No threshold temperature and activation energy could be defined in the case of poly( P-ethynyl naphthalene) where it is suggested that the driving force of isomerization lies in the constrained character of the cis-cisoidal helix. © 1985, Taylor & Francis Group, LLC. All rights reserved.

Publication Source (Journal or Book title)

Journal of Macromolecular Science: Part A - Chemistry

First Page

1001

Last Page

1011

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