Doctor of Philosophy
Joe B Gilroy
The work presented in this thesis details the synthesis and characterization of two different families of multifunctional polymers. The first family involved the incorporation of stable 6-oxoverdazyl radicals into polymer scaffolds. This was originally achieved by the polymerization of the radical precursors, phenyl- and isopropyl-6-oxotetrazanes, followed by post-polymerization oxidation to afford the phenyl- and isopropyl-6-oxoverdazyl polymers. A second methodology involved the direct polymerization of isopropyl-6-oxoverdazyl radicals using ring-opening metathesis polymerization (ROMP) to afford polymers with controlled molecular weights and narrow molecular weight distributions. The polymers were characterized by the close comparison of the physical and spectroscopic properties to related model compounds. The semiconducting behaviour of the latter polymer was explored and ultimately exploited in flash memory devices.
The second family included redox-active Ni(II) complexes of Goedken’s macrocycle. This macrocycle was incorporated into main-chain polymers via a step growth mechanism involving Sonogashira cross-coupling with π-conjugated solubilizing organic spacers and into side-chain polymers via a chain growth polymerization using ROMP. The resulting polymers spectroscopic and physical properties were characterized and compared to a variety of model compounds. Main-chain Ni(II) complexes of Goedken’s macrocycle and fluorene copolymers were further functionalized with Co2(CO)8 via the alkyne synthetic handle to yielded heterobimetallic copolymers that yielded metal-rich nanomaterials upon pyrolysis in a reducing atmosphere.
Combined, this work represents a significant advance in the synthesis, characterization and application of synthetic multifunctional polymers.
Paquette, Joseph A., "Synthesis of Metal-Containing Polymers and Stable Organic Radical-Containing Polymers and Their Use as Advanced Functional Materials" (2016). Electronic Thesis and Dissertation Repository. 4275.