This thesis describes the examination of novel block copolymers that contain Ru(bpy)32+ complexes incorporated into one block of diblock copolymers made by ROMP. With the intent of exploring the potential usefulness of these interesting materials in applications such as light-harvesting and sensing, a systematic study of the solution self-assembly, luminescence properties, and the ability of the metal complex to engage in electron and energy transfer reactions has been conducted. / The solution self-assembly of block copolymers that contain Ru(bpy) 32+ complexes was examined first. Using a series of these block copolymers, a detailed study of the effects of block length, block ratio, polymer concentration and solution conditions on the copolymer self-assembly is presented. Using TEM, a number of morphologies were reproducibly observed including star micelles, large compound micelles, tubules, and interestingly, vesicles. These structures all contain the metal complex Ru(bpy)3 2+ within their core domains. / The luminescence properties of two block copolymers containing Ru(bpy) 32+ were examined: one polymer self-assembled into star micelles, the other into vesicles. Comparison of the unassembled polymer chains and the self-assembled polymers indicated that self-assembly, and confinement of the Ru(bpy)32+ complexes into the core domains of the aggregates, did not seriously adversely affect the luminescence properties of the metal complex. Measurement of the luminescence lifetime decay of the polymers suggested that energy migration occurred among the metal complexes along the polymer chain. The ability of the metal complexes within self-assembled structures to participate in electron transfer reactions with small molecules was also explored. It was found that from within the core domains of self-assembled structures, the Ru(bpy)32+ complexes could still engage in electron transfer reactions with molecules on the outsides or the insides of the aggregates, likely a result of energy migration. / The ability of Ru(bpy)32+ complexes within the cores of micelles to participate in energy transfer was explored. Micelles were formed in aqueous solutions using polymers that possessed both the metal complex and a water-soluble block. Several methods were attempted to encapsulate two molecules, a derivative of coumarin 2 and an Os(bpy)3 2+-based molecule, inside these micelles. It was observed that Ru(bpy) 32+ could act as an energy acceptor from the coumarin derivative, and could act as an energy donor to the osmium-based complex. Encapsulation of the small molecules greatly enhanced the efficiency of energy transfer, by non-covalently bringing the small molecules in close proximity to the Ru(bpy)32+ complexes. / Polymers were synthesized that contained a Ru(bpy)3 2+-based block and were terminated with the molecular recognition unit biotin. These polymers, upon self-assembly, formed micelles with biotin groups on their periphery. The addition of the protein streptavidin, which has a strong binding affinity for biotin, resulted in the aggregation of the self-assembled structures. This established the potential for self-assembled metal-containing aggregates to form higher-order structures. / Early work is presented in Appendix A involving block copolymers that contain hydrogen-bonding groups. Several methods were attempted to elucidate the solution morphologies of these polymers, namely IR, 1H NMR, DLS, and pyrene fluorescence. The transition of this initial work to polymers that contain the Ru(bpy)32+ complex is also described.

Thermodynamic and kinetic analysis of the ligand substitution reactions of different heterometallic Ru(II)-Pt(II) complexes with a series of bio-relevant thiourea nucleophiles of different steric demands and ionic nucleophiles have been investigated as a function of concentration and temperature using UV/visible and stopped-flow spectrophotometric techniques. To achieve this, five different sets of complexes involving mono di and multinuclear homo and heterometallic complexes with tridentate N-donor ligands of different linker ligands were synthesized and characterized by various spectroscopic methods. The substitution reactions of the chloride complexes were studied in methanol in the presence of 0.02 M LiCf3SO3 adjusted with LiCl to prevent possible solvolysis. The aqua complexes were studied in acidic aqueous medium at pH 2.0. All reactions were investigated under pseudo first-order conditions. Density functional theory (DFT) calculations were used to aid further interpretations and understandings of the experimental results. Substitution reactivity of heterometallic Ru(II)-Pt(II) and Co(II)-Pt(II) complexes bridged by tetra-2-pyridyl-1,4-pyrazine (tppz) ligand was investigated for the first time. The reactions proceeded via two steps. The pseudo first-order rate constants, kobs(1st and 2nd) for the substitution of the chloride ligand(s) from the Pt(II) complexes and subsequent displacement of the linker. The dechelation step was confirmed by 1H NMR and 195Pt NMR studies. Incorporation of Ru(tppz) moiety increases the substitution reactivity and is ascribed to the increased π-back donation from the tppz ligand which increases the electrophilicity of the metal centre, overall charge and the global electrophilicity index of the complex. However, when changed the second metal centre from a Ru(II) to a Co(II), the rate of substitution decreased by a factor of four due to the weaker π- backbonding from Co(II). The substitution reactivity of another set of heterometallic Ru(II)-Pt(II) complexes with a semi-rigid linker, 4’-pyridyl-2,2’:6’,2”-terpyridine (qpy) showed that replacing the cis pyridyl group by a (tpy)Ru(qpy) moiety lowers the energy of anti-bonding LUMO (π*) orbitals and increases the metal-metal interactions and electronic transition within the complex whereby enhancing the reactivity of Pt(II) centre. However, when two Pt(II) moieties are linked to a (qpy)Ru(qpy), the orthogonal geometry at the Ru(II) metal centre prevents the extended π-electron density to flow through the three metal centres. The kinetic results obtained were supported by pKa and 195Pt NMR studies. Substitution reactions of the mononuclear Pt(II) complexes revealed that the polyethylene glycoxy pendent units act as a σ-donors including the lone pair electrons on the first oxygen atom thereby decreasing the reactivity of the parent Pt(II) terpyridine complex. However, this σ-donation towards the terpyridine moiety was found to be effective only up to one unit of the ethylene glycoxy pendant, beyond which the reactivity was sterically controlled. The dinuclear Pt(II) complexes bridged by polyehtyleneglycol ether units show that the reactivity of the complexes depend on the Pt···Pt distance and the steric hindrance at the Pt(II) centre. The substitution reactivity of heterometallic Ru(II)-Pt(II) complexes bridged by the same polyehtyleneglycol ether units indicate that the presence of Ru(tpy)2 moiety influences the structural geometry of the complex system which in turn controls the reactivity of the Pt(II) centre. This is further driven by the entrapment effect of the nucleophile due to the V-shape geometry adopted by the heterometallic complexes. In all cases the reactivity was also controlled by steric and electronic effects. However, when two metal centres are bridged by a flexible non-aromatic linker, the electronic transitions and the metal-metal interactions were found to be minor, especially for the longer linkers. The 1H and 195Pt NMR spectroscopic techniques were used to further understand the observed substitution kinetics and to confirm the degradation of the bridging ligand from the metal centre(s). In all cases, the negative activation entropies obtained support the associative mode of substitution This investigation reveals that the length and the nature of the bridging linker plays an important role in controlling the reactivity of the heterometallic complexes. It is envisaged that the findings of this project would offer a significant contribution to the pharmacological design of effective anticancer drugs. / Ph.D. University of KwaZulu-Natal, Pietermaritzburg 2013.

Thesis (Ph. D.)--University of Texas at Austin, 2007. / Vita. Includes bibliographical references.

Thesis (M. Sc.) (Hons.) -- University of Western Sydney, 2002. / A thesis presented to the University of Western Sydney in partial fulfilment of the rquirements for the degree of Master of Science (Honours), February, 2002. Includes bibliographical references.

Thesis (Ph. D.)--University of Hong Kong, 2007. / Title proper from title frame. Also available in printed format.

Thesis (Ph. D.)--University of Hong Kong, 2005.

Thesis (Ph. D.)--University of Hong Kong, 2004. / Also available in print.

Thesis (Ph. D.)--University of Texas at Austin, 2004. / Supervisor: Jack C. Lee. Vita. Includes bibliographical references.

Thesis (Ph. D.)--University of Hong Kong, 2006. / Also available online.

The oxidation of three alkyl thioethers, phenol and 2-propanol by trans-dioxo ruthenium porphyrin species, and the synthesis, characterization and reactivity of several new ruthenium porphyrin complexes are described in this thesis. The trans-dioxo species Ru(Porp)(O)₂ [Porp= the dianions of 5,10,15,20-tetramesitylporphyrin (TMP) and 5,10,15,20-(2,6-dichlorophenyl)porphyrin (OCP)] selectively oxidize diethyl-, di-n-butyl- and decylmethyl- sulfides to the corresponding sulfoxides at room temperature. The reaction is first order in [Ru] and in [thioether]. The second order rate constants for the first O-atom transfer from the Ru(TMP) system are: 7.54xl0⁻³, 1.23xl0⁻² and 1.14x10-¹ M⁻¹ s⁻¹ respectively for the three thioethers at 20.0 °C. The activation parameters for the O-atom transfer process are also determined: for Et₂S, ∆H‡= 58.3 kJ mol⁻¹ and ∆S‡= -86 J K⁻¹ mol⁻¹; for nBu₂S, AH‡= 47.4 kJ mol⁻¹and ∆S‡= -120 J K⁻¹ mol⁻¹; for DecMeS, ∆H‡= 56.5 kJ mo⁻¹ and ∆S‡= -70 J K⁻¹ mol⁻¹. A second order rate constant of 7.23xl0⁻²M⁻¹s⁻¹ is measured at 20.0 °C for the oxidation of Et₂S by Ru(OCP)(O)₂. The intermediates Ru(TMP)(OSEt₂)₂, Ru(TMP)(OSEt₂)(OSEt₂) and the final product Ru(TMP)(0SEt₂)₂,where O and S refer to O- and S- bonded sulfoxide, are observed by ¹H nmr, and the last mentioned is isolated and characterized. A mechanism is proposed, based on electrophilic attack of the O=Ru=O moiety on :SR₂ to form bis-O-bonded species which subsequently isomerizes to bis-S-bonded species via mixed species. The Ru(TMP)(O)₂/Et₂S/O₂ system at room temperature is catalytic in complex, but produces only about 5 turnovers due to poisoning of the catalyst by the reaction product. The same system at >65 °C gives higher turnovers, but now porphyrin ligand degradation is observed, perhaps via oxidation by the O=Ru=O moiety. The Ru(OCP)(0)₂/Et₂S/O₂ system at 100 °C catalytically oxidizes Et₂S to Et₂SO and Et₂SO₂ (in ~ 4:1 ratio) and the porphyrin ligand does not undergo oxidative destruction. The Ru(TMP)(O)₂ species reacts with phenol via an observed intermediate Ru(TMP)(p-O(H)C₆H₄OH)₂ to form Ru(IV)(TMP)(OC₆H₄OH)₂, a paramagnetic (S=l) complex which is isolated and characterized. The oxidation reaction is first order in both [Ru] and [phenol] with a second order rate constant 6.90x10⁻² M⁻¹ s⁻¹at 20.0 °C. A mechanism based on electrophilic attack by the O=Ru=O moiety on the aryl ring followed by proton migration is proposed. This mechanism also explains the formation of some free para-benzoquinone and 1 equivalent of water per Ru. No ortho-benzoquinone is formed in the reaction. Preliminary ⁻H nmr studies reveal that 2-propanol is oxidized to acetone by Ru(TMP)(O)₂. A paramagnetic species (S= 1) was isolated as the only porphyrin product but not characterized. A range of novel ruthenium porphyrin complexes is also prepared. The reaction of acetylene with the four-coordinate Ru(TMP) species forms [Ru(TMP)]₂(u-C₂H₂), the first reported organometallic ruthenium porphyrin dimer. The complexes, Ru(TMP)(PhCCPh) and Ru(TMP)(PhCCH), the first π-bonded alkyne species in ruthenium porphyrin chemistry, are characterized in solution. The π-bonded alkene complexes Ru(TMP)(CH₂CH₂) OPrOH).(iPrOH) and Ru(TMP)(CH₂CH₂) are isolated and characterized, while the Ru(TMP)(cyclohexene) complex is characterized in situ. The Ru(TMP)(OSEt₂)₂ complex is isolated also by the reaction of Ru(TMP)(CH₃CN)₂with Et₂SO. The Ru(TMP)(L)₂ complexes, L= OSMe₂, OSnPr₂ and OSnBu₂ are also prepared via the above method and characterized. Some new Ru(OCP) complexes, (the monocarbonyl, the bis-acetonitrile and the dioxo- species) are also isolated and characterized. / Science, Faculty of / Chemistry, Department of / Graduate