Approaches to ferrocene-containing pi-conjugated polymers: (synthesis, characterisation, structural and electrochemical studies)

Abstract

The aim of the work carried out for this thesis was to explore way to synthesise and characterise 𝛱-conjugated ferrocene containing polymers by using a condensation polymerization technique. Three types of such compounds were investigated: namely polyquinoxalines (pox)s, polyimines (PJ)s and polyketones (PK)s. The work was started by carrying out the same reactions on small molecules, in order to understand the reaction pathway and to establish the reaction conditions and to obtain the benchmark characterisation data. Initially monofunctional ferrocene derivatives were prepared and condensed with mono- and bi-functional organic molecules, and bifunctional ferrocene derivatives were synthesised and condensed with mono functional organic molecules, to yield the small molecular condensation products. When the reaction conditions had been optimised the same reactions were extended to bifunctional ferrocene derivatives and bifunctional organic entities to obtain the co-polymers. After citing the relevant references in chapter one, the synthesis of mono- and bi-functional ferrocene containing diketones (FcCOCOK) by the oxidation of the synthesised mono-ketones is described in chapter 2 and their condensation with unsubstituted and substituted organic di- and tetra-amines to produce ferrocene containing mono-, bis - and poly-quinoxalines is described in chapter 3. The crystal structures of some of the compounds are also determined as definitive proof of characterisation. The attempted oxidation offerrocenyl monoketones (FcCH2COK) to diketones by using selenium dioxide produced the coupled, dimeric, products (FcCHCOK)2. Electrochemical studies of the synthesised quinoxalines were also carried out. In chapter 4 are described the condensation of ferrocene aldehyde (FcCHO) and dialdehyde [(Fcd(CH0)2] with aromatic amines to yield ferrocene containing mono-, bis-and poly-imines. Chapter 5 deals with the synthesis and characterisation of ferrocene containing mono-, bis- and poly ketones synthesised by Friedel Crafts acytation reactions. The molecular weights of the synthesised ferrocene-containing polymers are also estimated with the help of hi NMR spectra.