Reduced state conducting polymers

• Main Author: Eastwick-Field, Vanessa Mary
• Published: University of Warwick 1991
• Subjects: 541; QD Chemistry
• Online Access: https://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.293928

The work presented in this thesis is concerned with reduced state conducting polymers, and in particular with poly(pyridine). The electroreductive polymerisation of 2,5-dibromopyridine based on either the Ni(0)(PPh3)4] or [Ni(0)(bpy)3ClO4)2] systems was investigated. The results obtained via both routes are discussed in terms of their respective mechanisms. The initial steps of the polymerisation based on the latter system are analysed using a specially developed kinetic theory. Although the theory was designed specifically to better understand the mechanism of electrosynthesis of poly(pyridine), it has a broader usage for the electrochemist because it describes the limiting current responses of second order ECE reactions at RDEs. The nature of poly(pyridine) prepared by both routes is investigated, and the results obtained are discussed in terms of their structural implications. Although the definitive nature of the polymers is still unclear, a particularly interesting possibility is that the polymers prepared from the [Ni(0)(bpy)3ClO4)2]/2,5-Br2Py/TEAP/AN system are “pyridylonickel strings”. The electrosynthesis of poly(azines) using the [Ni(0)(bpy)3ClO4)2]route is reported, and demonstrates that this strategy can be successfully exploited in the preparation of novel reduced state conducting polymers. Suggestions for further work forming an extension to this thesis are given in the final chapter.