This PhD project has expanded the knowledge in the area of profluorescent nitroxides with regard to the synthesis and characterisations of novel profluorescent nitroxide probes as well as physical characterisation of the probe molecules in various polymer/physical environments. The synthesis of the first example of an azaphenalene-based fused aromatic nitroxide TMAO, [1,1,3,3-tetramethyl-2,3-dihydro-2-azaphenalen-2-yloxyl, was described. This novel nitroxide possesses some of the structural rigidity of the isoindoline class of nitroxides, as well as some properties akin to TEMPO nitroxides. Additionally, the integral aromatic ring imparts fluorescence that is switched on by radical scavenging reactions of the nitroxide, which makes it a sensitive probe for polymer degradation. In addition to the parent TMAO, 5 other azaphenalene derivatives were successfully synthesised. This new class of nitroxide was expected to have interesting redox properties when the structure was investigated by high-level ab initio molecular orbitals theory. This was expected to have implications with biological relevance as the calculated redox potentials for the azaphenalene ring class would make them potent antioxidant compounds. The redox potentials of 25 cyclic nitroxides from four different structural classes (pyrroline, piperidine, isoindoline and azaphenalene) were determined by cyclic voltammetry in acetonitrile. It was shown that potentials related to the one electron processes of the nitroxide were influenced by the type of ring system, ring substituents or groups surrounding the moiety. Favourable comparisons were found between theoretical and experimental potentials for pyrroline, piperidine and isoindoline ring classes. Substitution of these ring classes, were correctly calculated to have a small yet predictable effect on the potentials. The redox potentials of the azaphenalene ring class were underestimated by the calculations in all cases by at least a factor of two. This is believed to be due to another process influencing the redox potentials of the azaphenalene ring class which is not taken into account by the theoretical model. It was also possible to demonstrate the use of both azaphenalene and isoindoline nitroxides as additives for monitoring radical mediated damage that occurs in polypropylene as well as in more commercially relevant polyester resins. Polymer sample doped with nitroxide were exposed to both thermo-and photo-oxidative conditions with all nitroxides showing a protective effect. It was found that isoindoline nitroxides were able to indicate radical formation in polypropylene aged at elevated temperatures via fluorescence build-up. The azaphenalene nitroxide TMAO showed no such build-up of fluorescence. This was believed to be due to the more labile bond between the nitroxide and macromolecule and the protection may occur through a classical Denisov cycle, as is expected for commercially available HAS units. Finally, A new profluorescent dinitroxide, BTMIOA (9,10-bis(1,1,3,3- tetramethylisoindolin-2-yloxyl-5-yl)anthracene), was synthesised and shown to be a powerful probe for detecting changes during the initial stages of thermo-oxidative degradation of polypropylene. This probe, which contains a 9,10-diphenylanthracene core linked to two nitroxides, possesses strongly suppressed fluorescence due to quenching by the two nitroxide groups. This molecule also showed the greatest protective effect on thermo-oxidativly aged polypropylene. Most importantly, BTMIOA was found to be a valuable tool for imaging and mapping free-radical generation in polypropylene using fluorescence microscopy.

A number of novel isoindoline nitroxides have been synthesised using a variety of synthetic techniques. Several carbon-carbon bond forming methodologies, including the first examples of Heck and Sonogashira coupling applied to the isoindoline nitroxide class, were utilised to give novel robust aromatic frameworks. Palladium-catalysed Heck coupling of brominated nitroxides and ester-substituted olefins generates novel nitroxides possessing extended conjugation. Hydrolysis of the nitroxide esters gave the corresponding carboxylic acids, which showed enhanced water solubility. Sonogashira coupling of an iodo-isoindoline nitroxide gave several novel alkynesubstituted nitroxides in high yield. Subsequent coupling of a deprotected ethynyl nitroxide with aromatic iodides gave acetylene-linked nitroxides and an acetylene linked nitroxide dimer. A butadiyne linked dinitroxide was successfully synthesised via Eglinton oxidative coupling of two ethynyl nitroxides. The synthesis of a novel water-soluble dicarboxy nitroxide was achieved by base hydrolysis of a dinitrile. Functional group interconversion furnished anhydride and imide substituted nitroxides from the diacid. Subjecting the imide to the Hofmann rearrangement gave an unexpected brominated amino-carboxy nitroxide. The dicarboxy nitroxide and the brominated amino-carboxy nitroxide were both shown to have a protective effect on Ataxia-Telangiectasia cells, indicating a possible role as antioxidants in the treatment of this disease. A fluorescein nitroxide was successfully synthesised through the condensation of the anhydride substituted nitroxide and resorcinol. After limited success using a variety of other techniques, Buchwald-Hartwig amination was able to furnish a rhodamine nitroxide, via a triflate-fluorescein nitroxide. The extended aromatic nitroxides possess suppressed fluorescence and we have described these systems as profluorescent. The profluorescent nitroxides were found to have significantly lower quantum yields than the non-radical analogues and displayed a substantial increase in fluorescence intensity upon radical trapping, making them useful probes for free radical reactions.