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<p> In an investigation on the formation of halogen cations, the I4 2+, Br3+, Br2+ and Cℓ3+ cations have been identified by conductivity, cryoscopy, ultraviolet and visible spectrophotometry, Raman spectroscopy and magnetic susceptibility measurements in strong acids. Bromine trifluorosulphate has been shown to ionise in the SbF5:3SO3/HSO3F system to give the Br(SO3F)2+ ion, and Raman bands of bromine fluorosulphates, CℓSO3F and S2O6F2 have been listed. No evidence has been found for the Cℓ2+ or CℓF+ ions in solution, and the assignment of observed ESR spectra to these cations is criticised.</p> <p> Raman spectra of the adducts AsF5 2CℓF and BF3 2CℓF have shown that they contain the CℓCℓF+ cation and not the CℓFCℓ+ cation. The bending frequency of the CℓF2+ cation has been reassigned, and force constants have been calculated for the CℓF2+ and Cℓ3+ cations.</p> <p> Resonance Raman spectra of the I2+ and Br2+ cations have been observed, and, as few examples of this effect are known, the variation in fundamental and overtone intensities with exciting wavelength have been investigated.</p> / Thesis / Doctor of Philosophy (PhD)

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Doctor of Philosophy / Department of Chemistry / Christer B. Aakeroy / The impact of the molecular electrostatic potential values (MEPs) in halogen and hydrogen bond interactions were explored using two acceptors with multiple acceptor sites with twelve hydrogen-bond donors, five halogen bond donors and four mixed halogen and hydrogen bond donors. The results suggested if the difference between the two acceptor sites is above 38 kJ/mol both hydrogen and halogen bond donors prefer the acceptor site with the highest MEP value and this selectivity was lost if the difference is below 26 kJ/mol. To examine the potential of halogen-bond donors in organocatalysis, a halogen-bond donor molecule was synthesized and the catalytic activity was measured using a benchmark Ritter type solvolysis reaction. Results suggested the catalytic activity of the halogen-bond donor molecule with > 90 % conversion of the product with the use of a stoichiometric amount of the catalyst for 96 hrs. Successful use of the control molecules confirm that the catalytic activity is an outcome of having halogen-bond donors in the molecule. The benefit of using a structural mimic in landscaping the structural outcomes of poorly soluble molecules was explored using an anticancer drug erlotinib. A structural mimic was synthesized by maintaining all binding sites that are important to design a structural landscape and the structural outcomes were analyzed using five FDA approved dicarboxylic acids. The results suggested that the structural outcomes of the mimic can be related to the actual drug erlotinib. Solubility and thermal behavior analysis of the co-crystals also suggested that with the systematic changes of the co-crystallization agent, it is possible to make predictable changes to the physical properties. To observe the effect of co-crystallization technology in reducing the chemical reactivity and sensitivity of an energetic compound dinitrobenzotriazole, a series of co-crystallization experiments was carried out using fourteen nitrogen and oxygen based acceptors. Four co-crystals were obtained and the acceptors were identified as supramolecular protecting groups which led to successful diminish of chemical instability and decreased impact sensitivity. Hygroscopicity and chemical reactivity of tetranitrobisimidazole, a potential RDX replacement, was successfully decreased by protecting the acidic N-H protons in the molecule by introducing suitable co-formers. Introduction of the N-oxide based acceptors into the system enhanced the stability while retaining most of the desirable energetic properties.

Noble gas and halogen data from a suite of Icelandic samples are presented. Iceland combines hotspot volcanism, a spreading ridge and abundant subglacially erupted samples. This combination allows for samples that erupted under high enough pressures to retain a measurable mantle volatile content, and also display signatures representing interaction between ocean island basalt (OIB) and mid-ocean ridge basalt (MORB) mantle sources.Erupted samples used to determine the mantle’s halogen and noble gas content have undergone a degassing process that can alter their volatile composition. An existing disequilibrium degassing model is developed with the modified model taking into account the evolution of the major volatiles over a multi-stage process and the different conditions present during magma ascent and quenching. The modified model allows substantially lower elemental noble gas ratios to be reached under disequilibrium conditions than allowed by the original model. Initial CO2 concentrations, pressure, diffusivity, ascent rate and degree of disequilibrium are shown to be critical parameters for this model. Final degassed noble gas concentrations are most affected by the surface quenching stage of an eruption, whereas noble gas elemental ratios can be primarily determined during magma ascent. In applying this model to MORB and OIB sample suites, the 3He/22Ne ratio of the MORB source mantle is constrained to be lower than 4.4, similar to estimates for the OIB source mantle. Additionally the most straightforward match between the degassing model and OIB helium and neon data suggest the OIB source mantle has 3He concentrations similar to or lower than the MORB source mantle. This finding requires a model for the OIB source mantle in which a high 3He/4He component is added to a helium-poor protolith.Noble gas studies are hampered by the large, isotopically atmospheric component typically found in Icelandic subglacial samples, which can swamp other signatures. Detailed analysis of a volatile rich sample from SW Iceland shows evidence for more than one ‘contaminant’ component and that two component fits used incorrectly can produce misleadingly precise source mantle noble gas ratios. Multi component best fits to noble gas elemental ratios find that four components are present in samples from this region. These components are unfractionated air, fractionated air and a mantle component which shows some variation due to degassing. Combining the disequilibrium degassing model with component resolution allows limits to be placed on the source mantle composition for this sample. The light noble gas source composition is compatible with mixing between a solar (‘direct nebula’) component and a MORB-like component. This direct nebula signature is at odds with an implanted signature seen in both Ne and Kr for the convecting mantle, and shows that both accretionary volatile origins must have contributed during the Earth’s formation. The heavy noble gases show an elemental abundance pattern which is distinct from air and solar patterns, and trends towards seawater. This confirms the presence of a recycled volatile signature in Iceland’s mantle but it is not possible to further constrain the origin of this signature.The Icelandic halogen data shows no evidence for significant fractionation during degassing or melt generation. Source estimates for the Br/Cl and I/Cl ratios for Iceland’s plume are found to be (1.56±0.03) x 10-3 and (3.1±0.3) x 10-5, compatible with estimates for the MORB source mantle. Halogen source concentrations in central Iceland are found to be approximately three times higher than estimates for the convecting mantle and correlate with the regions of Iceland that show high 3He/4He ratios and high source water contents. This may indicate a recycled halogen signature associated with Iceland’s proposed mantle plume.

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Information exchange is increasing rapidly with the advent of globalization. As the language spoken by the most people in today's world, Chinese will play an important role in information exchange in the future. Therefore, we need an efficient and practical means to access the increasingly large volume of Chinese data. This thesis describes a target-dominant Chinese-English machine translation system, which can translate a given Chinese news sentence into English. We conjecture that we can improve the state of the art of MT using a TDMT approach. This system has participated in the NIST (National Institute of Standards and Technology) 2004 machine translation competition. Experimental results on Penn Chinese Treebank corpus show that a machine translation system adopting a target-dominant approach is promising.

published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

The halogen bond has recently risen in prominence as a non-covalent interaction for use in supramolecular chemistry, allowing for the rational design of materials, pharmaceuticals, and functional molecules. The occurrence of the σ-hole opposite to the C-X covalent bond (X = F, Cl, Br, I) renders the halogen bond a highly directional and tuneable interaction, offering desirable features to crystal engineers. The halogen bond can be divided into its two components: the halogen bond donor bearing the halogen atom, and the electron-rich halogen bond acceptor. In this thesis, we investigate the nature of the halogen bond, its role in supramolecular assembly and impact on the local dynamics, along with developing synthetic methods to prepare this class of materials. We begin by fully characterizing the halogen bond donor by using 35Cl ultra-wideline solid-state nuclear magnetic resonance (NMR) spectroscopy on a series of single-component chloronitriles exhibiting the C-Cl···N halogen bond. We then perform the first modern nuclear quadrupole resonance (NQR) investigations of the halogen bond, observing the 79/81Br and 127I nuclei in a series of cocrystals exhibiting the C-Br···N and C-I···N halogen bond, respectively. Computational results attribute the observed increases in the quadrupolar coupling constants (CQ) to a reduction in the carbon-halogen σ-bonding contribution to V33 and an increase in the lone-pair and core orbital contributions, providing the first model of the electronic changes occurring on the halogen bond donor upon the formation of the halogen bond. Attention is then turned on characterizing the halogen bond acceptor and its surrounding environment, beginning by investigating a solid-state NMR approach relying on the 19F nucleus to characterize perfluorinated cocrystals. This strategy has reduced analysis times from hours to minutes while providing higher sensitivity and resolution, with the resulting chemical shifts permitting the unambiguous identification of the halogen bond and allowing for the refinement of X-ray crystal structures. The halogen bond acceptor is then investigated in a series of isomorphous dimers exhibiting both the halogen bond and hydrogen bond in the C≡C-I···X-···H-N+ motif, revealing the halogen bond’s relative contribution to the electric field gradient increasing in the order of Cl- > Br- > I-, contrasting the contributions of the hydrogen bond. We then explore the impact of the halogen bond on the surrounding environment, using the rotating methyl groups of 2,3,5,6-tetramethylpyrazine as a model. Upon the introduction of a halogen bond, we observe a reduction in the rotational energy barrier of 56% on average, overshadowing the 36% reduction observed in the hydrogen bonded cocrystals. This is the first instance of the halogen bond directly catalyzing the local dynamics, coining the term “dynamics catalyst”. These results provide an effective strategy of enhancing the dynamics in molecular systems, such as molecular machines, supramolecular catalyst, as well as correcting the faulty dynamics encountered in diseased proteins. The role of halogen bonding in crystal engineering is then explored, reporting the first supramolecular triangle, a series of discrete charged dimers, and supramolecular architectures built from 1,3,5-tri(iodoethynyl)-2,4,6-trifluorobenzene, with the potential of creating fully organic porous structures for gas absorption. Mechanochemistry is then investigated as a synthetic method, allowing for the preparation of cocrystals featuring 3-iodoethynylbenzoic acid as the donor, with the resulting structures exhibiting concurrent halogen and hydrogen bonding. Mechanochemical ball milling is shown to reduce preparation times of powdered cocrystals from days to a single hour, while using a fraction of the organic solvent. Lastly, we pioneer cosublimation as a solvent-free synthetic technique for rapidly preparing halogen bonded cocrystals, yielding quality single crystals within a few hours, and a microcrystalline product within 15 minutes. Among its advantages, cosublimation offers a significant acceleration of discovery, while eliminating the environmental footprint associated with conventional synthetic methods.