No description available.

No description available.

Pressure and temperature are two environmental variables that are increasingly being exploited by solid-state researchers probing structure-property relationships in the crystalline state. Modern high-pressure apparatus is capable of generating many billions of Pascals in the laboratory, and therefore can produce significantly greater alterations to crystalline materials than changes in temperature, which can typically be varied by only a few thousand Kelvin. Many systems such as single-molecule magnets exhibit interesting properties under low-temperature regimes that can be substantially altered with pressure. The desire by investigators to perform analogous single-crystal X-ray diffraction studies has driven the development of new high-pressure apparatus and techniques designed to accommodate low-temperature environments. [Ni(en)3][NO3]2 undergoes a displacive phase transition from P6322 at ambient pressure to a lower symmetry P6122/P6522 structure between 0.82 and 0.87 GPa, which is characterized by a tripling of the unit cell c axis and the number of molecules per unit cell. The same transition has been previously observed at 108 K. The application of pressure leads to a general shortening of O···H hydrogen bonding interactions in the structure, with the greatest contraction (24%) occurring diagonally between stacks of Ni cation moieties and nitrate anions. A novel Turnbuckle Diamond Anvil Cell designed for high-pressure low-temperature single-crystal X-ray experiments on an open-flow cryostat has been calibrated using the previously reported phase transitions of five compounds: NH4H2PO4 (148 K), ferrocene (164 K), barbituric acid dihydrate (216 K), ammonium bromide (235 K), and potassium nitrite (264 K). From the observed thermal differentials between the reported and observed transition temperatures a linear calibration curve has been constructed that is applicable between ambient-temperature and 148 K. Low-temperature measurements using a thermocouple have been shown to vary significantly depending on the experimental setup for the insertion wire, whilst also adding undesirable thermal energy into the sample chamber which was largely independent of attachment configuration. High-pressure low-temperature single-crystal X-ray diffraction data of [Mn12O12(O2CMe)16(H2O)4] (known as Mn12OAc) reveals a pressure-induced expulsion of the crystallized acetic acid from the crystal structure and resolution of the Jahn-Teller axes disorder between ambient pressure and 0.87 GPa. These structural changes have been correlated with high-pressure magnetic data indicating the elimination of a slow-relaxing isomer over this pressure range. Further application of pressure to 2.02 GPa leads to the expansion of these Jahn-Teller axes, resulting in an enhancement of the slow-relaxing magnetic anisotropy as observed in the literature. Relaxation of pressure leads to a resolvation of the crystal structure and re-disordering of the Jahn-Teller axes, demonstrating that this structural-magnetic phenomenon is fully reversible with respect to pressure. The space group of the Prussian blue analogue Mn3[Cr(CN)6].15H2O has been re-evaluated as R-3m between ambient pressure and 2.07 GPa using high-pressure single-crystal X-ray and high-pressure neutron powder data. Reductions in metal-metal distances and gradual distortions of the Mn octahedral geometry have been correlated with previously reported increases in Tc and declines in ferrimagnetic moment in the same pressure range. Increasing the applied pressure to 2.97 GPa leads to partial amorphization and results in a loss of long-range magnetic order as shown by the literature. The application of pressure (1.8 GPa) to the structure of K2[Pt(CN)4]Br0.24.3.24H2O (KCP(Br)) causes a reduction in the Pt intra-chain and inter-chain distances, and results in an enhancement of the overall conductivity under these conditions as demonstrated in the literature. Almost no changes occur to the high-pressure crystal structure upon cooling to 4 K, except in the Pt-Pt intra-chain distances which converge and suppress the Peierls distortion known to occur at 4 K, resulting in a comparatively greater electrical conductivity under these conditions.

This thesis will introduce the study of methane as a mineral. Along with ammonia and water, methane is one of the main planetary-forming materials in the outer solar system. The topic of `new mineralogy of the outer solar system' is outlined and introduced, and previous studies in the area are discussed. This review identities a lack of highpressure structural knowledge on methane when compared to ammonia and water. The significance of this knowledge for the study of the planets Neptune and Uranus is discussed. The crystal structures of methane above 5.2 GPa were, prior to this thesis, unknown. To tackle this long-standing problem an integrated approach of high-pressure diffraction techniques had to be used. The dominance of hydrogen within the structures of methane necessitated the use of neutron diffraction. The difficulties and limitations of highpressure neutron powder diffraction are presented. It will be shown that the complexity of the subsequent structures required the use of single-crystal x-ray diffraction. Using a combination of x-ray and neutron diffraction the structures of methane phase A (5.2 - 10 GPa) and B (10 - 25 GPa) were solved. The structure of phase A, was shown to conform to an indexing from literature [Nakahata 99] of a rhombohedral unit cell with α ≈ 89.3° and a ≈ 8.6 Å. Powder data were insufficient to determine atomic positions for this phase, and a single-crystal xray diffraction study was undertaken. The process of growing samples for this study is described as well as data collection. As a result of these studies the carbon atoms were located within methane phase A, and the density of the structure confined. The heavy atom structure, of phase A, was refined against neutron powder diffraction data, enabling positions of hydrogen atoms to be found. Preliminary powder diffraction studies of methane phase B found that the structure did not conform to the unit cell described within the literature. The phase was instead assigned to a cubic unit cell with a ≈ 11.73 Å. Similarly to the studies of phase A, a single-crystal x-ray diffraction study was undertaken. This was complicated by the presence of a contaminant within the sample area. This contaminant was shown to have no effect on the structural results. From a single-crystal study the heavy atom structure of phase B was found. The thesis charts the attempt, but ultimate failure, to obtain neutron powder diffraction on this phase. Comparisons of phase B with the higher pressure phase HP (25 GPa +) led to the conclusion that there would still be some disorder within the hydrogen atoms of phase B. Other studies have been carried out on the methane phase diagram. A Raman spectroscopy study, in the literature, on the low-temperature and high-pressure region of the phase diagrams (20 K up to 30 GPa) had suggested the existence of 3 additional phases of methane. A low-temperature, high-pressure neutron diffraction experiment was undertaken to try and characterise these phases. It was found that the phase A structure persisted under all conditions (to 20 K and 5 GPa) throwing the original results into question. During the growth of single-crystals for the above studies on phase A and B, a high-temperature solid-solid phase transition was observed. This transition line was mapped out and the phase resulting from it characterised with high-temperature single-crystal x-ray diffraction.

<p>This thesis is based on a study of five distinct intermetallic systems with the aim of expanding the general knowledge of aperiodically modulated crystal structures. Families of compounds that contain a variety of superstructures together with incommensurately modulated structures have been investigated mainly by means of single crystal X-ray diffraction and higher dimensional structure models.</p><p>A uniform (3+1)-dimensional structure for Bi-Se phases was developed with the composition as a single variable. The structure description is based on a cubic NaCl type structure with homoatomic layer stackings. It is shown by computational modelling that the formation energies of bismuth selenides with more than 40 at. % Bi are close to zero, a result that supports the idea of a continuous series of stackings corresponding to an ordered solid solution of Bi in Bi₂Se₃.</p><p>The Nowotny chimney-ladder structures are described with a (3+1)-dimensional composite structure, valid for all such compounds regardless of the included elements, the composition or the valence electron concentration. A new member is added to this family by the ZrBi_1.62 compound. The modulation is believed to arise as a secondary effect of the criteria of a fixed electron count.</p><p>A symmetry analysis is presented for the <i>RE</i>_1+ε(MB)₄ (<i>RE</i> = rare earth elements, M = iron metal elements) family of compounds and a uniform (3+1)-dimensional composite structure description has been developed. The modulation may be due to the presence of unusually short contacts between the <i>RE</i> channel atoms, giving rise to a rotational modulation of the (MB)₄ tetraederstern chains.</p><p>A (3+1)-dimensional incommensurate structure has been determined for the novel δ₁ – CoZn compound. The structure displays a unique assembly of fused icosahedra and the modulation is induced by geometric strain.</p><p>The structure of the K(PtSi)₄ compound was re-determined. Despite a close kinship with the <i>RE</i>_1+ε(MB)₄ compounds, this structure is not modulated.</p>

This thesis is based on a study of five distinct intermetallic systems with the aim of expanding the general knowledge of aperiodically modulated crystal structures. Families of compounds that contain a variety of superstructures together with incommensurately modulated structures have been investigated mainly by means of single crystal X-ray diffraction and higher dimensional structure models. A uniform (3+1)-dimensional structure for Bi-Se phases was developed with the composition as a single variable. The structure description is based on a cubic NaCl type structure with homoatomic layer stackings. It is shown by computational modelling that the formation energies of bismuth selenides with more than 40 at. % Bi are close to zero, a result that supports the idea of a continuous series of stackings corresponding to an ordered solid solution of Bi in Bi2Se3. The Nowotny chimney-ladder structures are described with a (3+1)-dimensional composite structure, valid for all such compounds regardless of the included elements, the composition or the valence electron concentration. A new member is added to this family by the ZrBi1.62 compound. The modulation is believed to arise as a secondary effect of the criteria of a fixed electron count. A symmetry analysis is presented for the RE1+ε(MB)4 (RE = rare earth elements, M = iron metal elements) family of compounds and a uniform (3+1)-dimensional composite structure description has been developed. The modulation may be due to the presence of unusually short contacts between the RE channel atoms, giving rise to a rotational modulation of the (MB)4 tetraederstern chains. A (3+1)-dimensional incommensurate structure has been determined for the novel δ1 – CoZn compound. The structure displays a unique assembly of fused icosahedra and the modulation is induced by geometric strain. The structure of the K(PtSi)4 compound was re-determined. Despite a close kinship with the RE1+ε(MB)4 compounds, this structure is not modulated.

Natural and synthetic common-rock forming minerals were examined using single-crystal X-ray diffraction (SXRD) and electron microprobe (EMP) analyses. The influences of common defect features, such as inclusions in spinel and oxygen positional disorder and twinning in kalsilite, were reported on the respective structures. The case studies show that these defect features could lead to a misinterpretation of X-ray intensity data. The structural interpretations obtained from these XSRD analyses could be significantly different when physical properties of the crystals are considered.In the second part of my dissertation, comparative crystal chemical studies on mantle-derived minerals such as spinel, clinopyroxene, and olivine are reported. These studies were carried out to examine temperature, pressure, and compositional effects on the structures of these phases. In particular, packing arrangements of oxygen atoms were examined in detail to investigate how the packing affects element partitioning among upper-mantle minerals. At ambient conditions, oxygen packing is more distorted in the order of spinel < olivine < clinopyroxene. The packing of oxygen atoms in olivine might have a significant control on element substitutions at high pressure. Because elements whose radius is larger than that of Mg distort the packing of mantle olivine (Fo~89), olivine might limit the amount of those elements, such as Fe2+, entering the structure. In contrast, substitutions of smaller cations in C2/c clinopyroxenes increase packing distortion. For clinopyroxenes enclosed in peridotite and eclogite, higher equilibration pressures are associated with more distorted, less efficiently packed structures. Unlike many minerals reported in Thompson and Downs (2001), spinel becomes more packed with rising temperature when intracrystalline cation exchange reactions are possible. Despite wide chemical variations, spinel samples from one geological environment display a constant packing distortion, which might suggest that spinel is capable of achieving an optimal packing configuration at a given P and T.

No description available.

This thesis extends our fundamental knowledge in the area of high oxidation state chemistry of xenon trioxide, XeO3. Oxygen coordination to the Xe(VI) atom of XeO3 was observed in its adducts with triphenylphosphine oxide, [(C6H5)3PO]2XeO3, dimethylsulfoxide, [(CH3)2SO]3(XeO3)2, pyridine-N-oxide, (C5H5NO)3(XeO3)2, and acetone, [(CH3)2CO]3XeO3. The crystalline adducts were characterized by low-temperature single-crystal X-ray diffraction and Raman spectroscopy. Unlike solid XeO3, which detonates when mechanically or thermally shocked, the solid [(C6H5)3PO]2XeO3, [(CH3)2SO]3(XeO3)2, and (C5H5NO)3(XeO3)2 adducts are insensitive to mechanical shock, but undergo deflagration when exposed to a flame. Both [(C6H5)3PO]2XeO3 and (C5H5NO)3(XeO3)2 are air-stable at room temperature. The xenon coordination sphere in [(C6H5)3PO]2XeO3 is a distorted square pyramid and provides the first example of a five-coordinate Xe center in a XeO3 adduct. The xenon coordination sphere of the remaining adducts are distorted octahedral comprised of three equivalent Xe---O secondary contacts that are approximately trans to the primary Xe–O bonds of XeO3. Hirshfeld surfaces of XeO3 and (C6H5)3PO in [(C6H5)3PO]2XeO3 show the adduct is well-isolated in its crystal structure and provide a visual representation of the secondary Xe---O bonding in this adduct. Crown ethers have been known for over 50 years, but no example of a complex between a noble-gas compound and a crown ether or another polydentate ligand had been reported. Xenon trioxide is shown to react with 15-crown-5 to form the kinetically stable (CH2CH2O)5XeO3 adduct which, in marked contrast with solid XeO3, does not detonate when mechanically shocked. The crystal structure shows that the five oxygen atoms of the crown ether are coordinated to the xenon atom of XeO3. The gas-phase Wiberg bond valences and indices and empirical bond valences indicate the Xe---Ocrown bonds are predominantly electrostatic, σ-hole, bonds. Mappings of the electrostatic potential (EP) onto the Hirshfeld surfaces of XeO3 and 15-crown-5 in (CH2CH2O)5XeO3 and a detailed examination of the molecular electrostatic potential surface (MEPS) of XeO3 and (CH2CH2O)5 reveal regions of negative EP on the oxygen atoms of (CH2CH2O)5 and regions of high positive EP on the xenon atom that are also consistent with σ-hole bonding. Reactions of crown ethers with HF acidified aqueous solutions of XeO3 at room-temperature yielded adducts of 12-crown-4, (CH2CH2O)4XeO3, and 18-crown-6, [(CH2CH2O)6XeO3∙2H2O]2∙HF, whereas slow cooling of a solution of XeO3 with 18-crown-6 in acetone yielded (CH2CH2O)6XeO3∙2H2O. The adducts (CH2CH2O)4XeO3 and (CH2CH2O)6XeO3∙2H2O are shock-insensitive whereas the former adduct is air-stable at room temperature. The low-temperature, single-crystal X-ray structures show the Xe atom of XeO3 coordinated to the oxygen atoms of the crown ether ring. Uncharacteristic xenon coordination numbers exceeding six (including the three primary bonds of XeO3) were observed for all crown ether adducts. Raman spectroscopy frequency shifts are consistent with complex formation and provided evidence for the 2,2,1-cryptand adduct of XeO3. Gas-phase Wiberg bond valences and indices and empirical solid-state bond valences confirmed the electrostatic nature of the Xe---O bonding interactions. Comparisons between the XeO3 and SbF3 18-crown-6, 15-crown-5, and 12-crown-4 complexes are made. Incorporation of xenon trioxide, XeO3, into inorganic polyatomic salts under ambient conditions has been observed in several mixed xenate salts; K[XeO3XO3] (X = Cl, Br), K2[XeO3SeO4]∙HF, K[(XeO3)nZO3] (Z = I, N), and M2[(XeO3)nCO3]∙xH2O (M = Na, K, Rb, Ba). Raman spectroscopy was used to identify the aforementioned compounds and K[XeO3ClO3], K[XeO3BrO3], K2[XeO3SeO4]∙HF, and Rb2[(XeO3)2CO3]∙2H2O were also characterized by low-temperature, single-crystal X-ray diffraction. The xenon atom of XeO3 is seven coordinate in K[XeO3ClO3] and six coordinate in all other compounds with Xe---O distances that are significantly less than the sum of the Xe and O van der Waals radii. These salts provide examples of XeO3 coordinated to inorganic compounds and may provide insights into the inclusion of xenon oxides in minerals. / Thesis / Master of Science (MSc)

Poly-aryl, also known as polyphenylene compounds are a class of dendrimer, which contain a large number of aromatic rings. They are of interest because they display restricted rotation of their stearically congested aromatic rings. These extended structures have the potential to act as precursors for even larger aromatic systems and have many applications including electronic devices, drug delivery and catalysis. A total of 23 novel poly-aryl compounds have been examined using single crystal X-ray diffraction and a number of structural patterns have emerged. Six of the compounds contain alkynes and it has been observed that their conformation is governed by a combination of conjugation between the alkyne and aryl groups and inter-molecular interactions. In the more extended poly-aryl compounds steric congestion rules out any possibility of conjugation between the rings and their conformation is governed by intra-molecular non-bonded interactions in the core of the molecules and by inter-molecular interactions in their periphery. Where possible, solution NMR measurements were carried out on the poly-aryl compounds and confirmed that the solution structures are in agreement with those obtained from individual crystal.