This thesis project has focused on the development of high-pressure single-crystal diffraction experiments on the neutron Laue diffractometer KOALA at the OPAL reactor at ANSTO, Australia. Over the course of this project several candidate systems have been studied under conditions of high-pressure using X-ray diffraction with a view to their use in developmental experiments on KOALA. The results of two high-pressure KOALA experiments are presented as well as the notable results from X-ray diffraction on the candidate systems. The first experiment on hexamethylenetetramine provided valuable insights into how reduced crystallite size and reciprocal-space access affects data collected on KOALA. In addition, data treatment techniques were developed to deal with the unique and challenging high-pressure Laue data, including corrections for attenuation due to the cell body. The ability to collect data through the body of cell prompted a further experiment on the complex, low-symmetry structure of the amino acid l-arginine dihydrate. Despite the smaller crystal size and dominant parasitic scattering from the diamond-anvil cell, the data collected allow a full anisotropic refinement of hexamethylenetetramine with bond lengths and angles that agree with literature data within experimental error. This technique is highly suited to low-symmetry crystals, as shown by the successful refinement of data from a l-arginine dihydrate crystal. In such cases the transmission of diffracted beams results in higher completeness values than are possible with X-rays. The hydrogen-bonded ferroelectric rubidium hydrogensulfate was the subject of ambient-pressure experiments on KOALA investigating the nature of the ferroelectric transition. Further high-pressure X-ray diffraction studies were carried out to resolve the structures of phases at high-pressure and to investigate the ferroelectric transition under pressure. The potassium cobalt citrate metal-organic framework UTSA-16 has shown a wide variety of pressure-mediated framework-solvent interactions including negative linear compressibility, the ordering of potassium ions, and coordination changes which were investigated by high-pressure single-crystal and powder X-ray diffraction. These behaviors are rationalised by examination of the structural changes occurring in the framework under pressure. Two members of the widely studied alkylammonium tetrachlorometallate family, tetramethylammonium tetrachloroferrate(III) and tetramethylammonium tetrachlorogallate(III), display numerous phase transitions with temperature. The structures of these phases have been determined for the first time, and the contrast between the two materials explored with first-principles calculations.

The spinel structure (general formula AB2O4) is widely occurring in natural and synthetic materials, and has a marked technological and scientific significance due to its magnetic, electric and multiferroic behaviours. The presence of transition metal cations with multiple oxidation state and the resulting charge, orbital and spin degrees of freedom of the partially occupied d-orbitals lead to uniquely ordered ground states. The coupling of all the three degrees of freedom can result in a structurally distorted ground state where the direct metal-metal interaction forms atomic clusters, or 'orbital molecules'. The Verwey phase of magnetite (Fe3O4), occurring below TV ~ 125 K, is driven by a cooperative bond distortion that forms linear Fe3+-Fe2+-Fe3+ arrangement (trimeron). The effect of non-stoichiometry and chemical modification on this complex structure has been investigated with a variety of samples through microcrystal synchrotron XRD. A mineral sample (Al, Si, Mg and Mn impurities, TV = 119 K) confirms the Verwey phase as the most complex long-range electronic order known to occur naturally; its relevance in space sciences is discussed. Moreover, the structural analysis of two synthetic magnetites (Fe3(1-δ)O4 with 3δ = 0.012 and TV = 102 K, Fe3-xZnxO4 with x = 0.03 and TV = 90 K) univocally confirmed the persistence of the transition, and its first order, at doping level > 1 %, contrary to previous reports. Moreover, the temperature evolution of the trimerons and their persistence above TV was probed through X-ray Pair Distribution Function analysis on pure Fe3O4: the data analysis between 90 K < T < 923 K show that the Verwey phase goes from long-range ordered (T < 125 K) to short-range ordered (T > 850 K). Magnetite can thus only be considered to have a regular cubic spinel structure above the Curie temperature (TC = 858 K). The pyrochlore lattice of B cations in a spinel gives the structure the potential for frustration upon antiferromagnetic ordering. Fe2GeO4 and γ-Fe2SiO4 were synthesised through conventional solid state routes, with the use of high-pressure synthesis for the latter. Magnetometry and heat capacity measurements highlighted two transitions (Tm1 = 8.6 K and Tm2 = 7.2 K, and Tm1 = 11.2 K and Tm2 = 7.5 K respectively). Powder neutron diffraction data between 2 K < T < 25 K showed that both materials stay undistorted below TN. Magnetic Rietveld refinement led to two highly unconventional magnetic structures, with incommensurate propagation vectors and modulation of the moment magnitude. γ-Fe2SiO4 also shows a spin-ice order below Tm2. The results are unique and unusual for transition metal oxides; the models are systematised by proposing a 'frustration wave' model, in which the degree of frustration is a spatial quantity that can be distributed through the structure in order to stabilise the ground state.

With reference to some figures reproduced in this thesis: "Readers may view, browse, and/or download material for temporary copying purposes only, provided these uses are for noncommercial personal purposes. Except as provided by law, this material may not be further reproduced, distributed, transmitted, modified, adapted, performed, displayed, published, or sold in whole or part, without prior written permission from the American Physical Society." / We report on the growth and characterization of strontium ruthenate (214) (Sr2RuO4) and strontium rhodate (214) (Sr2RhO4) in efforts to test their agreement with Landau-Fermi liquid theory using optical measurements. We begin by reviewing the theory of Landau-Fermi liquids and the frequency and temperature dependent conductivities. We review existing work on both Sr2RuO4 and Sr2RhO4 including evidence of agreement with Landau-Fermi liquid theory. We also describe optical floating zone crystal growth and the exact procedures we used to prepare samples of both Sr2RuO4 and Sr2RhO4 via optical floating zone. The resulting Sr2RuO4 crystals were characterized using AC susceptibility measurements and Sr2RhO4 by powder diffraction, single crystal diffraction, and SQUID magnetization measurements. Finally, early optical reflectivity measurements at low temperatures are presented. / Thesis / Master of Science (MSc) / Crystals of Sr2RuO4 and Sr2Rho4 were grown by the author in an effort to study changes of their resistivity with varying temperature and frequency at low temperatures. The crystals were characterized using a variety of x-ray and other techniques, so as to measure their purity. Past work on these materials is discussed and analyzed. Preliminary measurements of the resistivity are presented.