AbstractThe research discussed in this thesis involves the synthesis, characterisation, and properties of σ-bound metallopolymers containing nickel or cobalt, alongside supramolecular polymers containing cobalt or gold.
Chapter 1 gives context to the results presented in this thesis by broadly discussing a variety of polymerisation techniques. This introduction also aims to highlight relevant metallocenecontaining and metallosupramolecular polymer examples.
Chapter 2 describes the synthesis and ROP of [n]nickelocenophanes to produce
polynickelocenes with silicon and carbon main-chain spacers. To access soluble high molar mass materials, copolymerisations of the various monomers were performed. Characterisation of the magnetic properties of the [n]nickelocenophanes and homopolymers by SQUID magnetometry is also described.
Chapter 3 evaluates the thermodynamic parameters for ROP of the [n]nickelocenophanes described in Chapter 2 using DFT calculations. The syntheses of various other [n]nickelocenophanes and their propensity to ROP are also described. Finally, the effect on the thermodynamic parameters for ROP of adding a subsistent to the ansa bridge of tricarbanickelocenophane was explored.
Chapter 4 encompasses two projects: firstly, the application of poly(cobaltoceniumethylene) materials in the protection of β-lactam antibiotics. Additionally, the syntheses of novel cobaltocenium-containing polymers is described, including both traditional σ-bound polymetallocenes as well as supramolecular cobaltocenium-containing polymers.
Chapter 5 describes the synthesis and supramolecular self-assembly of three gold(I)-containing complexes with subtle core structural differences. The energy landscapes of polymerisation were determined, and rationalised with reference to the extent of core conjugation.
Chapter 6 presents ongoing projects and potential avenues for future work, based on the results detailed in Chapters 2–5.
|Date of Award||7 May 2019|
|Supervisor||Ian Manners (Supervisor) & George Whittell (Supervisor)|