The supramolecular chemistry and crystal structures of four Bis(imidazolium 2,4,6-pyridinetricarboxylate) metal(II)dihydrate complexes, where M=Co2+, Ni2+, Cu2+, or Zn2+ (1-4, respectively), are reported. These complexes serve as supramolecular building blocks that self-assemble when crystallized to generate a single, well defined structure in the solid state. 2,4,6-Pyridinetricarboxylate anions and imidazolium cations form strong ionic hydrogen bonds that dominate crystal packing in compounds 1-4 by forming three-dimensional (3-D) networks of molecules. These networks consist of hydrogen-bonded layers of molecules defined by N-H…O interactions that are joined in the third dimension by O-H…O interactions. This 3-D network provides a supramolecular framework with which to control and predict molecular packing by design for engineering the structures of crystals. Furthermore, compounds 1-4 create a robust organic host lattice that accommodates a range of different transition metals without significantly altering the molecular packing. Growth of crystals from solutions that contain two or more different metal complexes results in the formation of mixed crystals in which the different metal complexes are incorporated into the crystalline lattice in the same relative molar ratio present in solution. Epitaxial growth of crystals involving deposition of one metal complex on the surface of a seed crystal that contains a second metal complex generates composite crystals in which the different metal complexes are segregated into different regions of the crystals. Compounds 1-4 form crystalline solids that represent a new class of modular materials in which the organic ligands serve as a structural component that defines a single packing arrangement that persists over a range of structures, and in which the metal serves as an interchangeable component with which vary the physical properties of material.

Nanoscale structural characterization is critical to understanding the physical underpinnings of properties and behavior in materials with technological applications. The work herein shows how the pair distribution function technique can be applied to x-ray total scattering data for material systems which weakly scatter x-rays, a typically difficult task due to the poor signal-to-noise obtained from the structures of interest. Characterization and structural modeling are demonstrated for a variety of molecular and porous systems, along with the detection and characterization of disordered, minority phases and components. In particular, reliable detection and quantitative analysis are demonstrated for nanocrystals of an active pharmaceutical ingredient suspended in dilute solution down to a concentration of 0.25 wt. %, giving a practical limit of detection for ordered nanoscale phases within a disordered matrix. Further work shows that minority nanocrystalline phases can be detected, fingerprinted, and modeled for mixed crystalline and amorphous systems of small molecules and polymers. The crystallization of amorphous lactose is followed under accelerated aging conditions. Melt quenching is shown to produce a different local structure than spray drying or freeze drying, along with increased resistance to crystallization. The initial phases which form in the spray dried formulation are identified as a mixture of polymorphs different from the final α-lactose monohydrate form. Hard domain formation in thermoplastic polyurethanes is also characterized as a function of methylene diphenyl diisocyanate and butanediol component ratio, showing that distinct and different hard phase structures can form and are solved by indexing with structures derived from molecular dynamics relaxation. In both cases, phase fractions can be quantified in the mixed crystalline and amorphous systems by fitting with both standards or structure models. Later chapters, demonstrate pair distribution characterization of particle incorporation, structure, and synthesis of nanoporous materials. Nanoparticle size distributions are extracted from platinum nanoparticles nucleating within a zeolite matrix through structural modeling, and validated by transmission electron microscope studies. The structure of zirconium phosphonate-phosphate unconventional metal organic framework is determined to consist of turbostratically disordered nanocrystalline layers of Zr-phenylphosphonate, and the local environment of terbium intercalated between the layers is found to resemble the local environment in scheelite-type terbium phosphate. Finally, the early stages of reaction between aqueous zinc dinitrate hexahydrate and methanolic 2-methylimidazole are characterized using in situ total scattering measurements, showing that secondary building units of tetrahedrally coordinated by 2-methylimidazole initially form upon reaction. Overall, the methodologies are developed and applied toward phase detection, identification, solution, and behavior in pharmaceuticals, polymers, and nanoporous materials along with advice for carrying out experiments and analysis on such materials such that they can be extended to other similar systems.

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Mesoporous titania molecular-sieve thin films have been modified by incorporating guest species either in the pores or on the walls of the structure. The incorporation was realized with the aid of sonochemical processing. The structure, morphology, texture, optical properties, and stability of the resulting nanostructures were characterized by X-ray diffraction, nitrogen adsorption, UV-vis diffuse reflectance spectroscopy, infrared spectroscopy, photoluminesent spectroscopy, scanning electron microscopy, transmission electron microscopy, thermalgravimetric and differential thermal analyses. The photocatalytic and catalytic properties of the mesoporous TiO2-based nanocomposites were evaluated by photocatalytic degradation of organic pollutants, photo-assisted killing of bacteria/cancer-cells, and catalytic oxidation of carbon monoxide. / The thesis includes seven parts. The first part describes the pore-wall chemistry and photocatalytic activity of mesoporous nanocrystalline TiO 2 molecular sieve films. The ordered mesoporous TiO2 films show better photocatalytic activities than do the conventional sol-gel-derived TiO2 films toward the degradation of volatile organic pollutants. The reasons for the high activities of the mesostructural films are also discussed. The second part of the thesis reports the incorporation of highly dispersed gold nanoparticles in the mesoporous TiO2 films by a sono- and photochemical approach. The gold nanoparticles thus obtained are well-confined and stabilized in the nanopores of the TiO2 film and therefore, the intrinsic agglomeration of gold nanoparticles is prevented. This eliminates the use of potentially catalyst-poisoning organic ligands for stabilization. This method can also be used to prepare ordered mesoporous Pt/TiO2 and Ag/TiO2 nanocomposites with catalytic and photocatalytic functions as described in the third and forth parts of the thesis. In the fifth part, solid superacid molecular sieves are prepared by the wall-functionalization of the TiO2 film by sulfate groups with the aid of sonication. The resulting 3D-ordered mesoporous sulfated TiO2 superacid molecular sieve films are found to be attractive photocatalysts for environmental applications. The sixth part the thesis reported the sonodeposition of poorly dissolved phthalocyanine dyes onto the surface of the TiO2 film. The dye molecules are attached and stabilized in the pores of the film, avoiding the aggregation of the dye molecules, and consequently achieving effective photosensitization of the TiO2 film. The final part of the thesis describes the preparation of hierarchically macro/mesoporous TiO2 nanostructural photocatalysts. The existence of macroporous channels in a mesoporous TiO2 material improves the photoabsorption efficiency and matter-transfer. These enhance the photocatalytic performance of the bimodal porous TiO2 nanocomposites toward degradation organic pollutants in gas-phase. (Abstract shortened by UMI.) / Wang Xinchen. / "July 2005." / Adviser: Jimmy C. Yu. / Source: Dissertation Abstracts International, Volume: 67-01, Section: B, page: 0293. / Thesis (Ph.D.)--Chinese University of Hong Kong, 2005. / Includes bibliographical references. / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Electronic reproduction. [Ann Arbor, MI] : ProQuest Information and Learning, [200-] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Abstracts in English and Chinese. / School code: 1307.

Research to design and synthesise new porous materials is a rapidly growing field with thousands of new systems proposed every year due to their potential use in a multitude of application in a wide range of fields. Pressure is a powerful tool for the characterisation of structure-property relationships in these materials, the understanding of which is key to unlocking their full potential. In this thesis we investigate a range of porous materials at a range of pressures. Over time the chemical architecture and complexity of porous materials has increased. Although some systems display remarkable stability to high-pressures, which we generally think of as being above 1 GPa (10,000 bar), in general, the compressibility of porous materials have increased substantially over the last 10 years, rendering most unstable at GPa pressures. Here we present new methods for investigating porous materials at much more moderate pressures (100's of bar), alongside more traditional high-pressure methods (diamond anvil cell techniques), finishing with gas sorption studies in a molecular based porous material. Here, the design and development of a new moderate pressure sapphire capillary cell for the small molecule beamline I19 at the Diamond Light Source is described. This cell allowed access to pressures of more than 1000 bar regularly with a maximum operating pressure of 1500 bar with very precise pressure control (< 10 bar) on both increasing and decreasing pressure. This cell closes the gap between ambient pressure and the lowest pressures attainable using a diamond anvil cell (DAC), which is generally above 0.2 GPa (2000 bar). Along with the development of the sapphire capillary pressure cell, the compression to 1000 bar of the small organic sample molecule Hexamethylenetetramine (hexamine, C6H12N4) and its deuterated form (C6D12N4) was determined, demonstrating the precision possible using this cell. Solvent uptake into porous materials can induce large structural changes at 100's of bar. In the case of the Sc-based Metal-organic framework (MOF), Sc2BDC3 (BDC = 1,4-benzenedicarboxylate), we used the sapphire capillary pressure cell to study changes in the framework structure on the uptake of n-pentane and isopentane. This work shows how the shape and smaller size of n-pentane facilitated the swelling of the framework that could be used to explain the increase in stability of the MOF to applied pressure. The effect of pressure on the previously unreported Cu-framework bis[1-(4- pyridyl)butane-1,3-dione]copper(II) (CuPyr-I) was investigated using high-pressure single-crystal diffraction techniques (DAC). CuPyr-I was found to exhibit high-pressure and low-temperature phase transitions, a pressure induced Jahn- Teller switch (which was hydrostatic medium dependent), piezochromism, and negative linear compressibility. Although each of these phenomena has been reported numerous times in a range of materials, this is to the best of our knowledge the first example to have been observed within the same material. The final two chapters investigate the exceptional thermal, chemical, and mechanical stability of a porous molecular crystal system (PMC) prepared by the co-crystallisation of a cobalt phthalocyanine derivative and a fullerene (C 60 or C70). The stabilising fullerene is captured in the cavity between two phthalocyanines in a ball and socket arrangement. These PMCs retain their porous structure: on the evacuation of solvent of crystalisation; on heating to over 500 K; on prolonged immersion in boiling aqueous acid, base, and water; and at extreme pressures of up to 5.85 GPa, the first reported high-pressure study of a PMC. the reactive cobalt cation is accessible via the massive interconnected voids, (8 nm3), as demonstrated by the adsorption and binding of CO and O2 to the empty metal site using in situ crystallographic methods available at beamline I19, Diamond Light Source.

Two foams, a polyether (density 32.5 kg/m3) and a polyester (density 38 kg/m3) foam were tested in a shock tube to analyze the interaction of a normal shock wave and a compressible porous material. The foam specimens were placed in the shock tube test section! the foam being bounded by two steel walis, two glass windows and a solid back plate. The compression chamber of the shock tube was pressurized and the diaphragm separating the compression chamber and the expansion chamber was ruptured, thus producing a normal shock wave which travels down the shock tube and strikes the foam. Piezoelectric pressure transducers 'vvera used to record the pressure before, alongside and behind the foam. A complete set of schlieren photographs, recording the interaction of the incident shock wave and the porous material were taken for each foam. A method ,tortracking the path of particles of foam (path photographs) was developed. Combining the information obtained from the pressure records, schlieren photographs and path photographs a complete picture of the shock wave foam interaction was developed. All the gas waves were identified and analyzed, A foam wave (velocity 90 m/s) travelling through the skeleton of the material was discovered. A physical model was developed to explain the high pressure recorded behind the foam. This model is based upon the foam being compressed and forming an almost solid piston, thus forcing the trapped gas into a diminishing volume and creating a high pressure behind the foam. The theoretical analyses of Monti (30), Gel'fand (20) and IBvozdeva (22) were analyz.ed and compared. The general finding was that for the range of incident mach numbers 1.~i1 to 1.46 Monti's analysis under predicts the reflected Mach number by 3 % and Gel'fand's analysis over predicts the reflected Mach number by 6 %. The coefficient of pressure increase (the ratio of the maximum pressure recorded behind the foam to the equivalent pressure recorded during ~he reflection of a shock wave from a solid wall) as predicted iJy Gvoz.deva's ane.lysisfor the polyether foam lies wjthin the scatter of the experimental results. However for the polyester foam Gvozdeva's analysis under predicts the coefficient of pressure increase by 15%. / GR 2016

Silk fibroin from silkworm cocoons is found in numerous applications ranging from textiles to medical implants. Its recent adoption as a biomaterial is due to the material's strength, biocompatibility, self-assembling behavior, programmable degradability, optical clarity, and its ability to be functionalized with antibodies and proteins. In the field of bioengineering it has been utilized as a tissue scaffolding, drug delivery system, biosensor, and implantable electrode. This work suggests a new application for porous silk in a microscale chromatography column. We demonstrate in situ cryotropic polymerization of highly porous structures in microscale geometries by freezing aqueous silk with a solvent. The resulting cryogels are experimentally characterized using flow parameters common in chromatography design; tortuosity, global pressure drop, pore diameter, and porosity. These empirical parameters are put into porous flow models to calculate an order-of-magnitude increase in functional surface area over the blank capillaries and packed-sphere columns used in traditional designs. Additionally, the pressure requirements to produce relevant flow rates in these structures are found not to threaten the integrity of microfluidic seals or connectors.

Transition metals have been extensively studied as catalysts, and certain metals are known to be highly selective and active for certain processes. It is possible to use metal clusters as models for reactions occurring at metal surfaces, but it is often found that in practical applications these complexes are unstable and break down. It is possible to support or stabilise a metal species on, or in, an inorganic framework, making heterogeneous catalysts. A study of metal cluster chemistry with mixed-donor phosphine ligands was conducted, with several new ruthenium complexes synthesised. The chemistry of metal-sulfur interactions is applicable to the removal of sulfur from crude oil, and in an investigation to this chemistry, the bifunctional ligand HSCH2CH2PPhH was added to ruthenium clusters (Chapter 2). The addition of this sulfur-phosphine ligand to the cluster [Ru3([mu]-dppm)(CO)10] produced the carbonyl substituted cluster [Ru3([mu]-dppm)(H)(CO)7(SCH2CH2PPhH)] and the bridged complex [Ru3([mu]-dppm)(H)(CO)8(SCH2CH2PPhH)Ru3([mu]-dppm)(CO)9], as well as recovery of the starting material. Further reactions with this ligand were examined with [Ru3(CO)12] and other complexes were synthesised with different clusters and ligands (Chapter 2). The M41S materials, MCM-41 and MCM-48, are well ordered porous materials with high surface areas (Chapter 3). The incorporation of three different types of metal species, metallosurfactants, metal clusters and nanoparticles, into these materials was examined in an attempt to make heterogeneous catalysts for the Fischer-Tropsch process. The success of this was studied using characterisation techniques such as powder X-ray diffraction, transmission electron microscopy and BET surface area measurements. Metallosurfactants containing either copper or cobalt were added directly to the synthesis of the porous materials in an attempt to incorporate the metals into the framework structure of the porous silica (Chapter 3). This resulted in well ordered iv porous materials, but the successful incorporation of the metal species was found to be dependent on several factors. Organometallic clusters containing metals such as copper, iron and ruthenium, with supporting carbonyl ligands, were added post-synthesis to MCM-41 and MCM-48 (Chapter 4). Various reaction conditions were examined in attempts to ensure small particle formation. The optimum incorporation of nanoparticles containing iron and platinum was found to occur when a suspension of pre-made and purified nanoparticles was added post-synthesis to the M41S materials (Chapter 4). These materials resulted in porous silicas with well dispersed, small metal particles. The optimum conditions for the calcination of these new materials were determined, in an attempt to remove the ligands and stabilisers and retain the small metal particle size (Chapter 5). Testing for the Fischer-Tropsch process was conducted in a fixed bed reactor through which a flow of synthesis gas containing carbon monoxide and hydrogen could pass over the material (Chapter 5). Analysis by gas chromatography showed that the major product produced by all materials tested was methane, but other hydrocarbons were produced in small amounts, including hexane.

Shocked porous granular material experiences pressure dependent compaction. D. John Pastine introduced a model in which the degree of compaction is dependent on the pressure induced by the shock wave, the shear strength of the material, and the distribution of void sizes. In the past, the model could only be approximated. Using computational techniques and higher speed computers, the response of this model to void size distributions may be displayed to a high degree of precision. / Graduation date: 1996