The investigation in this thesis focuses on the synthesis of cation-ordered perovskite phases by introducing anion vacancies into the structure. Complex cation-ordered phases Ba2YMO5 and Ba3YM2O7.5 (M = Fe, Co) have been synthesized using ceramic or citrate gel methods under flowing argon. Close inspection reveals that the structures are constructed from Y2M2O102 basic units which consist of two YO6 octahedra and two MO4 tetrahedra in a rock-salt type arrangement. In the structure of Ba2YMO5 (M = Fe, Co), the neighbouring Y2M2O102 units are connected with an equivalent one in the yz-plane with YO6 octahedra sharing an apex. In the structure of Ba3YM2O7.5 (M = Fe, Co), the basic units are connected to each other by the M2O7 dimers via a chain of Y – O – M – O – M – O – Y bonds. Complex cation ordering can be achieved by carefully controlling the anion vacancies and selecting the cations with different ionic radii. The anion vacancies present in Ba2YMO5 (M = Fe, Co) (space group P21/n) allow the intercalation of anions like O2- and F- into the lattice. The fluorination of Ba2YCoO5 leads to the formation of a new orthorhombic phase Ba2YCoO5F0.42 (space group Pbnm) in which the inserted fluoride ions are distributed in a disordered manner. In contrast, the topochemical oxidation of Ba2YFeO5 leads to the formation of a new orthorhombic phase Ba2YFeO5.5 (space group Pb21m), in which Fe4+ centres are located in 4-coordinate tetrahedral sites and 5-coordinate pyramidal sites, respectively. The polar structure of Ba2YFeO5.5 is confirmed by the observation of second-harmonic generation activity and pyroelectric behaviour. Ba2YFeO5.5 also exhibits a combination of ferromagnetic and antiferromagnetic behaviours at low temperature. LaCa2Fe2GaO8 adopts a six-layer structure consisting of an OOTLOOTR stacking sequence of layers of (Fe/Ga)O6 octahedra (O) and (Fe/Ga)O4 tetrahedra (T), related to that of the four-layer brownmillerite structure (space group Pbma). The chains of tetrahedra in the structure of LaCa2Fe2GaO8 exhibit a cooperative twisting distortion in which the twisting direction of the chains of tetrahedra alternates in adjacent tetrahedral layers. LaxSr2-xCoGaO5+δ (0.5 < x < 1) adopts brownmillerite structures which consist of octahedral and tetrahedral layers with mixed valence of Co2+/Co3+. The members with x = 0.5, 0.6 and 0.7 adopt structures with I2mb space group symmetry, in which all the tetrahedra twist in the same direction. The members with x = 0.8, 0.9 and 1.0 adopt structures with Imma space group symmetry, in which the chains of the tetrahedra twist in a disordered manner. A change in the Co3+ spin state from high spin (HS) to low spin (LS) is observed as the La/Sr ratio increases. The change of the Co3+ spin state can be rationalized on the basis of internal chemical pressure.

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published_or_final_version / abstract / Biological Sciences / Master / Master of Philosophy

Nitric oxide (NO) has been shown to both suppress and promote tumor growth, depending in part on concentration. Exogenous delivery of NO may lead to tumor suppression. Recent studies have proposed ruthenium nitrosyl complexes as catalytic donors of NO in reductive environments. Catalytic donation can provide a long-term, elevated NO flux compared to single use donors. Site-specific delivery is desirable to reduce systemic side effects, such as lowering of blood pressure. Three new ruthenium nitrosyl complexes were synthesized to impart site-specificity through amide coupling to polymers, silica nanoparticles, iron oxide nanoparticles and antibodies. The catalytic activity of new and existing compounds was then assessed. However, upon one-electron reduction of ruthenium nitrosyl complexes, insignificant amounts of NO were detected, suggesting an alternative mechanism than that proposed in prior reports. The mechanism of [Ru(EDTA)NO]²⁻ decay was more thoroughly analyzed. Spectrophotometric decay of [Ru(EDTA)NO]²⁻ indicates that one or multiple nitrogen oxide species are released. Previous studies have suggested a disproportionation mechanism leading to the generation of more highly reduced species such as N₂ and NH₄⁺. Experiments were designed to analyze possible decomposition products such as [Ru(EDTA)NO]⁻ and [Ru(EDTA)H₂O]²⁻. A disproportionation mechanism was determined likely. Decomposition of [Ru(EDTA)NO]²⁻ was also observable following reductive nitrosylation of [Ru(EDTA)H₂O]⁻ in the presence of HNO. The decomposition product, [Ru(EDTA)H₂O]²⁻, was observed through the binding of pyrazine (pz) or dipyridine (bipy) and formation of [Ru(EDTA)pz]²⁻ or [Ru(EDTA)bipy]³⁻. Formation of [Ru(EDTA)bipy]³⁻ or [Ru(EDTA)pz]²⁻ via reductive nitrosylation of [Ru(EDTA)H₂O]⁻ also provides an indirect method of HNO detection that is selective from NO.

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Transition metal oxide thin films are commonly used in organic electronics devices to improve charge-injection between electrodes and organic semiconductors. Some oxides are good hole-injectors, while others are good electron-injectors. Transition metal oxides are materials with many diverse properties. Many transition metals have more than one stable oxidation state and can form more than one oxide. Each oxide possesses its own unique properties. For example, transition metal oxide electronic band structures can range from insulating to conducting. They can exhibit a wide range of work functions. Some oxides are inert, while others are catalytically active. Such properties are affected by numerous factors, including cation oxidation state and multiple types of defects. Currently it is not fully understood which oxide properties are the most important to their performance in organic electronics. In the present thesis, photoemission spectroscopy is used to examine how changes in certain oxide properties–such as cation oxidation states and defects—are linked to the oxide properties that are relevant to organic electronics devices—such as an oxide’s work function and electron band structure. In order to unravel correlations between these properties, we controllably change one property and measure how it changes affects another property. By performing such tests on a wide range of diverse transition metal oxides, we can discern broadly-applicable relationships. We establish a relationship between cation oxidation state, work functions and valence band structures. We determine that an oxide’s electron chemical potential relative to an organic’s donor and acceptor levels governs energy-level alignment at oxide organic interfaces. We establish how interfacial reactivity at electrode/oxide interfaces dictates an oxide’s work function and electronic structure near the interface. iii These findings demonstrate some of the very interesting fundamental relationships that exist between chemical and electronic properties at interfaces. These findings should assist in the future development and understanding of the functional interfaces of organic semiconductors and transition-metal oxides.

Spin and orbital orderings are amongst the most important phenomena in the solid state chemistry of oxides. Physical property and powder neutron and X-ray diffraction measurements are reported for a range of mostly low dimensional ternary transition metal oxides which display spin or orbital order. Extensive studies of the physical properties and crystal structure of In2VO5 are reported. The structure of this material consists of one dimensional zig-zag chains of orbitally ordered S = 1/2 V4+. Magnetic susceptibility measurements show an unusual crossover from dominant ferromagnetic (θ = 17 K) to antiferromagnetic (θ = -70 K) exchange at 120 K, which is attributed to ferromagnetic dimerisation driven by magnetic frustration. The magnetic moment also increases from 1.81 to 2.2μB at the 120 K crossover. Heat capacity measurements confirm this scenario as the magnetic entropy tends towards 1/2 Rln3 below 120 K before approximating to Rln2 at high temperature. Synchrotron x-ray diffraction and high resolution neutron powder diffraction show no bulk structural changes, but the b axis, along which the VO6 chains run, shows an anomalous expansion below 120 K. At low temperatures, a downturn in the magnetic susceptibility is seen at 2.5 K, signifying a spin freezing transition. Heat capacity and powder neutron diffraction measurements show no evidence for long range magnetic order down to 0.42 K. The low dimensional brannerite materials MV2O6 (M = Mn, Co, Ni) were synthesised by a sol-gel method. Magnetic properties were investigated by magnetisation, powder neutron diffraction and in the case of CoV2O6, heat capacity measurements. The structure of these materials consists of linear chains of edge sharing MO6 octahedra. Monoclinic MnV2O6 is an isotropic antiferromagnet with TN = 20 K and a reduced magnetic coherence length due to 3 % Mn/V antisite disorder. The magnetic structure consists of ferromagnetic edge-sharing chains with k = (0,0,1/2) and a refined Mn moment of 4.77(7) μB. The triclinic materials CoV2O6 and NiV2O6 are also antiferromagnetic with TN = 7 and 14 K respectively and both show metamagnetic type transitions. Unusually, M(H) isotherms recorded below 5 K for CoV2O6 show a plateau at 1/3 of the saturation magnetisation. This feature, together with a long period modulated magnetic structure, is attributed to strong single ion (Ising) type anisotropy and nearest neighbour ferromagnetic exchange. Preliminary high pressure experiments on NiV2O6 have confirmed a previously reported transition to a columbite phase at 6 GPa and 900 °C. The high pressure polymorph is also antiferromagnetic with TN = 2.5 K. The previously uncharacterised perovskite, PbRuO3 has been prepared using high pressure/temperature synthesis techniques (10 GPa, 1000 °C). Synchrotron powder X-ray diffraction measurements show that the room temperature structure is orthorhombic, Pnma. A first order orbital ordering transition occurs at 75 K with an associated metal insulator transition. Below 75 K, the dxz orbitals are preferentially occupied and the structure is orthorhombic Imma. The transition may be driven by an increase in antiferroelectric Pb2+ displacements, whcih reach a peak at ~ 125 K. A further structural transition to a larger monoclinic cell is also identified at 9.7 K. The physical properties and crystal structures of two low dimensional lead manganese oxides have also been investigated. Acentric Pb2MnO4, which has a structure consisting of edge sharing chains, is antiferromagnetic with TN = 18 K. Powder neutron diffraction shows the magnetic structure consists of antiferromagnetic chains with k = (0,0,0) and a refined Mn moment of 2.74(2) μB. The crystal point group allows piezoelectricity and the magnetic point group symmetry allows piezomagnetism. We speculate that coupled magnetic and electric properties may be observed in this material. The layered material, Pb3Mn7O15, with a structure consisting of 1/2 filled Kagomé layers has also been studied. Single crystals were prepared by a flux growth method and polycrystalline material was prepared by the ceramic method. Powder neutron and synchrotron x-ray diffraction studies show that the single crystals are hexagonal and that the polycrystalline material is orthorhombic. Furthermore, heat capacity measurements show that the hexagonal single crystal material undergoes a glassy magnetic transition. In contrast, powder neutron diffraction shows that the orthorhombic polycrystalline material has coherent long range magnetic order. These differences are attributed to an oxygen deficiency in the polycrystalline magnetic order. These differences are attributed to an oxygen deficiency in the polycrystalline material.