This thesis describes the effects of the application of high pressure to single crystals of small organic compounds. A range of different structural analysis techniques have been used with the emphasis on whole molecule interactions rather than atom-atom contacts. A study of the effect of pressure on the crystal structure of salicylaldoxime showed that the size of a pseudo-macrocyclic cavity within the structure is tuneable by compression. This cavity determines the reactivity of salicylaldoxime as a ligand, when deprotonated it is known to preferentially bind Cu 2+ ions over other cations in a bis(salicylaldoximato) complex due to the compatibility between the cavity size and the ionic radius of Cu 2+. Further compression studies on a range of substituted salicylaldoximes with different ambient cavity sizes showed that the application of pressure consistently decreases the cavity size across the whole series. Variation of substituent and the pressure yields cavities which span the covalent radii of many of the 1st transition series metal dications. This should allow the selectivity of metal extraction to be tuned using pressure. Computational studies of lattice energies and conformational energies in the compression studies of L-serine and 3-aza-bicyclo(3.3.1)nonane-2,4-dione have shown that significant molecular distortions can occur during compression of a crystal structure below 10 GPa. L-serine shows different conformations between phases with an energy difference of 40 kJ mol-1, whereas the conformation of 3-aza-bicyclo(3.3.1)nonane-2,4-dione is seen to distort within the same phase. Analysis of a database of compression studies using Hirshfeld surfaces has highlighted the fact that all different types of intermolecular interaction have a lower limit for compression, at least in the pressure regime below 10 GPa. These studies, along with theoretical calculations, have suggested a lower distance limit for H…H contacts of 1.7 A. This is potentially very useful for prediction of the effects of compression as H…H contacts are almost universal across small organic crystal structures.

Increasing the efficacy of ligands is crucial to many industrial processes and products. The design of new organic reagents which might find applications in automotive lubrication and extractive metallurgy are reported. Force-field based molecular modelling has been used in chapters 2 and 3 to investigate the structure of complexes of malonic acids and benzohydroxamic acids formed on binding to iron(III) oxide surfaces for which both have shown high affinity. Models were constructed in which the ligands were docked to planes in the lepidocrocite crystal structure to simulate their interaction with steel engine surfaces. The Cambridge Structural Database has been used to elucidate the structures of polynuclear complexes of carboxylic acids to define appropriate geometries for malonate complex models. The most plausible modes of surface binding involving malonic acid were modelled to establish which would show the most favourable ligand-surface and ligand-ligand secondary bonding. Modelling of hydroxamate surface binding was guided by structural motifs observed in a mononuclear trishydroxamato iron(III) complexes in a dinuclear complex [Fe2L2(μ2L)2Br2] where LH = benzohydroxamic acid. The resulting model predicted the surface activity of a range of hydroxamic acid derivatives which have been confirmed by measurements of adsorption isotherms carried out on high surface area goethite. The structures of square planar copper(II) complexes of 3-substituted salicylaldoxime ligands which are closely related to systems used in industrial hydrometallurgical processes have been investigated (chapter 4) to ascertain whether there are correlations between the solid state structures and the relative strengths of the ligands as copper extractants. It was expected that electronegative groups would enhance hydrogen bonding between ligands, pulling them towards one another with a consequent decrease in the binding cavity presented by the donor atoms. In practice the structures were found to be influenced by interactions present in the solid state. In particular, axial interactions were found to influence the inner coordination sphere geometry and these were also investigated (chapter 5) using high pressure X-ray crystal structures. Contrary to expectation, application of pressure was found to increase axial bond lengths in order to improve molecular packing efficiency so that the cell volume could decrease.

Thesis (M.Sc.) - Carleton University,2001. / Includes bibliographical references. Also available in electronic format on the Internet.

Ba0.5Sr0.5Co0.8Fe0.2O3-delta (BSCF) and SrCo0.48Fe0.12Ti0.4O3-delta (SCFT) were synthesised by co-precipitation. BSCF was pressed and sintered at 1100℃ for 10 hours to pellets (relative density: 93%) from which X-ray diffraction (XRD) revealed single Pm-3m phase (a=3.9782 A). Scanning electron microscopy (SEM) revealed clear equiaxed grains (grain size 33 ± 16 micro metre). The pellets were decomposed in 7 ± 1 % CO2/N2 at 800℃ for 1 to 30 minutes. XRD confirmed secondary phases: R-3mH phase (a=b=5.1397 A, c=9.4847 A) and Fm-3m phase (a=4.2490 A). Electron backscattered diffraction (EBSD) ascribed R-3mH and Fm-3m phases to the surface and part of the cross-section precipitates, respectively as revealed by SEM. Energy dispersive X-ray spectroscopy (EDX) revealed the compositions of R-3mH and Fm-3m phases to be Ba0.65±0.03Sr0.35±0.03CO3 (BSC) and CoO, respectively. Transmission electron microscopy (TEM) and EDX revealed the structure (15R, R3m and R-3mH) and composition (Ba0.20Sr0.10Co0.59Fe0.10Ox) of lamellar precipitates in cross-section, suggesting Ba and Sr diffuse from the lamellae to BSC. A unique orientation relation (BSCF {111} // BSC {0001}) was uncovered by EBSD. TEM revealed high symmetry contact planes of lamellae and BSCF, suggesting nucleation energy governs decomposition. Fresh BSCF pellets were decomposed in N2 at 800℃. Fm-3m and P63/mmc phases were confirmed by XRD and lamellae were observed by SEM, followed by decomposition in 7±1 % N2/CO2 at 800℃. XRD revealed higher weight % of BSC and CoO. SEM revealed BSC preferring lamellae, hence hexagonal phases accelerated BSC formation. BSCF pellets were dip coated in SCFT propan-2-ol suspension (3:10), followed by sintering at 1165℃ for 10 hours. XRD revealed a Pm-3m phase (a=3.885 A) and SEM revealed a grain size of 65 ± 9 micro metre and open porosity of 1.6 ± 1 %. They were annealed in 7 ± 1 % CO2/N2 at 800℃. XRD revealed no secondary phases, suggesting enhanced stability. However, oxygen permeability was reduced (1.2 ml/cm2 to 0.8 ml/cm2) because the coating composition changed to Ba0.20Sr0.27Co0.40Fe0.10Ti0.04Ox; this was revealed by EDX.

The group 14 Zintl clusters [E₉]⁴⁻ (E = Ge, Sn, Pb) have been reacted with organometallic reagents in solution in the presence of alkali metal cation sequestering agents. The synthesis, characterisation and reactivity studies of the resultant complexes are reported herein. These negatively charged clusters reductively cleave one of the M–C bonds in the group 12 homoleptic organometallic reagents MR₂ (M = Zn, Cd; R = Ph, mes, ⁱPr) to yield η⁴-coordinated functionalised clusters closo-[E₉MR]³⁻. They can also activate both of the M–C bonds in Cd(mes)₂ to form metal-bridged dimers [Ge₉CdGe₉]⁶⁻ and [Pb₉CdCdPb₉]⁶⁻. Investigating the reactivity of the functionalised cluster [E₉CdPh]³⁻ (E = Sn, Pb) towards HSn(ⁿBu)₃ results in the synthesis of the novel closo-clusters [E₉CdSn(ⁿBu)₃]³⁻. The reaction of K₄Ge₉ with the heteroleptic organometallic reagent Fe(COT)(CO)₃ yields the metalated cluster anion [Ge₈Fe(CO)₃]³⁻, in which the nuclearity of the Zintl anion is altered upon coordination of the [Fe(CO)₃] moiety. Two side products have also been isolated as [K(2,2,2-crypt)]⁺ salts of [Fe(η³-C₈H₈)(CO)₃]⁻ and [Fe₂(η³, η′³-C<sub<16</sub<H₁₆)(CO)₆]²⁻. In the presence of highly reduced Zintl anions, all the M–C bonds in homoleptic mid-row transition metal organometallic reagents can also be cleaved. These ‘naked’ metal atoms have templated the formation of the endohedral clusters [Fe@Ge₁₀]³⁻, [Fe@Sn₁₀]³⁻ and [Mn@Pb₁₂]³⁻. These clusters adopt very different geometries and the electronic origin of their structures has been investigated in-depth by DFT calculations. Structural characterisation of some side products is also reported for: [E₉(mes)]³⁻ (E = Ge, Sn) and [Ge₉Mn(mes)]³⁻.

Framework materials that contain molecular bridging ligands between metal nodes—as seen in coordination polymers—not only give rise to enhanced structural diversity, but also to a range of useful and unusual mechanical properties. This thesis demonstrates the general structure–property relationships that are developed for coordination polymers in order to enable prediction and design of their mechanical properties, and hence structural flexibility. Variable-temperature and -pressure diffraction experiments are employed for the determination of their mechanical properties, namely by calculating thermal expansion and compressibility coefficients. The anomalous and varied mechanical responses observed are rationalised by the important structural features, or the so-called mechanical building units (XBUs), of the coordination polymers. The XBUs are considered within the setting of framework topology, geometry, and composition in order to establish general design principles for targeting different degrees of flexibility within coordination polymers. The XBUs are identified first in silver(I) 2-methylimidazolate, Ag(mim), a framework which is comprised of structural motifs of varying strength, namely argentophilic interactions, hinge points and metal–ligand bonding. The anomalous mechanical responses in Ag(mim) are shown to be rationalised entirely by the XBUs present in the structure. The XBU abstraction is then applied to a range of other coordination polymers and shown to correspond directly with the anomalous responses known in these materials. The metal–ligand–metal linker XBU is investigated further in both cadmium imidazolate, Cd(im)₂, and zinc cyanide, Zn(CN)₂. Here, the linker chemistries are completely different between the two frameworks, but the diamondoid arrangement of the linkers, and thus the topology, is the same. The structural responses of the two frameworks are examined to unravel the extent of topology- and chemistry-driven mechanics. It is found that the topology dominates the atomic displacements of both frameworks, indicating the existence of common soft-mode dynamics which are likely to extend to other coordination polymers with the same topology. The three-dimensional framework-hinging XBUs in zinc isonicotinate, Zn(ISN)₂, and indium deuterium terephthalate, InD(BDC)₂, are considered next. These frameworks have the same topology but contrasting framework geometries, evident from the differing c/a-lattice parameter ratios. In this case, a geometric formalism is derived which can predict the direction of framework mechanical anisotropy in Zn(ISN)₂ and InD(BDC)₂ and other uniaxial coordination polymers. Finally, a family of ABX₃-type transition metal(II) formates are investigated, where both the B-site and A-site cations are varied. The chemical modifications give rise to variations in B- or A-site cation sizes, which are found to correlate with the magnitude of mechanical responses. These structure–mechanical property relationships—based upon framework topology, geometry and composition—are presented in separate chapters, and in each case generalised so that they can be applied to a range of coordination polymers. Hence the design principles determined here can provide the materials science community with an intuition on the type and magnitude of responses possible in these materials under different external stimuli.

The research presented within this thesis is concerned with the design, synthesis, characterisation, and analysis of a series of new compounds of platinum (II), with aims to produce compounds possessing switchable optical properties, and with potential applications as "smart-materials" for use as highly selective sensors.

No description available.

This thesis describes the synthesis, characterisation and reactivity of diamide-amine and bis(cyclopentadienyl) supported Group 4 hydrazido(2-) compounds towards unsaturated molecules. The mechanisms of these transformations are probed using a range of structural, kinetic and computational methods.

Farnesyl pyrophosphate synthase (FPPS) is a key branch point enzyme in the mevalonate pathway and the main molecular target of nitrogen-containing bisphosphonates (N-BPs), potent inhibitors of osteoclastic activity and the leading drug of choice for conditions characterized by excessive bone resorption. The main aim of this thesis is to investigate the interaction of N-BPs with FPPS in order to gain further insights into the mechanism of drug inhibition. Kinetic and crystallographic studies following site-directed mutagenesis of FPPS reveal key residues involved in stabilization of carbocation intermediate, substrate binding and formation of a tight enzyme-inhibitor complex. The aromatic ring of Tyr204 is involved in N-BP binding but not in the catalytic mechanism, where the hydroxyl moiety plays an important role. Lys200 is implicated in regulation of substrate binding, product specificity and enzyme isomerization which leads to a tight binding inhibition. Phe239 is considered important for the FPPS C-terminal switch which stabilizes substrate binding and promotes the inhibitor induced isomerized state. The highly conserved Arg112, Asp103 and Asp107 are pivotal for catalysis. Successful purification of the full length of Rab geranylgeranyl transferase (RGGT) complex downstream of the FPPS in the mevalonate pathway was achieved and may lead to co-crystallization with BP analogues and identification of the putative site of drug binding. Investigation of the in vitro effect of N-BPs on osteoclastogenesis suggest a correlation with FPPS inhibition kinetics for the most potent N-BPs but indicate an alternative mechanism of the disruption of bone resorption by alendronate. Together these results highlight the importance of the multiple interactions of N-BPs with side-chain residues of FPPS which dictate their strength of binding and advance the understanding of their pharmacophore effect.