Debye-Scherrer x-ray powder photography is used to study the dependence of the host lattice parameters of LixMoCO₂ (0 ≤ x≤ 1) upon the lithium content (x). The results indicate that the host lattice expands considerably as x increases but that the lattice reassumes its original structure when the lithium is removed. Intercalating one equivalent of lithium (x = 1) causes a considerable (~13%) increase in the unit cell volume. This expansion is confined to directions perpendicular to the tunnels through the MoO₂ lattice. Detailed measurements are made of the voltage V(x) of Li/LixMoO₂ cells. These and the x-ray patterns both indicate that LixMoO₂ occurs in three distinct compositional phases with approximate compositions of MoO₂, Li1/2MoO₂ and LiMoO₂. First-order transitions involving pronounced hysteresis effects are observed as the lithium content is altered. A brief discussion of the electrochemical properties of the LixMoO₂ system in terms of a lattice gas model is included. / Science, Faculty of / Physics and Astronomy, Department of / Graduate

This thesis identifies and discusses physical mechanisms in intercalation batteries. The effects of interactions and ordering of intercalated atoms on the voltage behaviour of intercalation cells is described, largely in terms of the lattice gas model of intercalation. Particular emphasis is given to the mean field solutions of the lattice gas model, which are compared to more exact solutions for several cases. Two types of interaction between intercalated atoms are discussed, namely electronic and elastic interactions; it is found that both can be important in intercalation compounds. The kinetics of intercalation batteries is also discussed, with emphasis on overpotentials due to diffusion of the intercalated atoms in the host lattice. Experimental studies of the voltage behaviour of three types of lithium intercalation cells, Li[sub=x]TiS₂, Li[sub=x]MoO₂, and Li[sub=x]MoS₂, are presented, which illustrate the variety of voltage behaviour found in intercalation cells. / Science, Faculty of / Physics and Astronomy, Department of / Graduate

This thesis describes experimental methods, including in situ X-ray diffraction, especially suited to the study of lithium intercalation systems,and discusses the interpretation of the results obtained in a study of Li[sub=x]TiS₂. A rigid plate and spring model of layered intercalation systems is developed and is used to investigate the role of lattice expansion and elastic energy in layered intercalation compounds. When the elastic energy, calculated using the spring and plate model, is included in the Hamiltonian of a three dimensional lattice gas model for Li[sub=x]TiS₂ good agreement between the experimental results and the theoretical predictions are obtained. Staging, not lithium ordering, is identified as the dominant physical mechanism in Li[sub=x]TiS₂. / Science, Faculty of / Physics and Astronomy, Department of / Graduate

Includes bibliographical references. / The synthesis and characterization of a series of inorganic coordination compounds which, upon crystallization, have the ability to include solvent or guest molecules spatially within the lattice are reported. The compounds have the following general formula: [NiX2B4] - where X is isothiocyanate or bromine and B is 4-ethylpyridine, 4-vinylpiridine or 3,5-dimethylpyridine; [NiX2B2]n - where X is isothiocyanate, B is 2-aminopyridine and n indicates it is a polymer; [NiX2AB2]2 - where X is isothiocyanate, B is 3-aminopyridine (two of these four ligands in the dimer are bridging) and A is water. The various guest molecules have been carefully chosen, according to their point symmetry, which is a key factor in yielding structures of a particular type. The structures of seventeen compounds have been elucidated by single crystal x-ray analysis. The difficulty has been found to lie in refining disordered guest molecules. Other techniques employed in the initial characterization of these compounds are Microanalysis, Mass Spectrometry and UV/Visible Spectrophotometry. An intramolecular potential energy study on the [Ni(NCS)2(3,5-diMepy)4] complex reveals that the orthohydrogens on the 3,5-dimethylpyridine ligands control the conformation of the molecule. Packing densities and volume comparisons of the [Ni(NCS)2(4-Etpy)4] and [Ni(NCS)2(4-Vipy)4] complexes and their clathrates have been carried out. The exact sizes and shapes of the cavities in which the guest molecules are located in the x-ray crystal structures have been evaluated by both intermolecular potential energy and molecular volume calculations. Thermodynamic and spectroscopic properties of the [Ni(NCS)2(4-Etpy)4] and [Ni(NCS)2(4-Vipy)4] clathrates have been studied in both solution and the solid state. The techniques used are x-ray powder diffractometry, IR spectroscopy and Thermogravimetry (including Differential Thermal Analysis).

The crystal structures of Ni(NCS)₂(4-ViPy)₂.nG where nG = 2CH₂Cl₂ (I), 2CCl₄ (II), 1.8CH₂I₂ (III) and CHI₃ (IV), as well as the crystal structure of [Ni(NCS)₂(4-ViPy)₄]. [Ni(NCS)₂(4-ViPy)₃(thf)].2CHI₃ (V) have been elucidated. The diiodomethane guest molecules in STRUCTURE III were severely disordered at room temperature and so this structure was solved at -40°C. The dichloromethane clathrate is isomorphous with the chloroform clathrate of the same host, and both these clathrates have a similar packing to the carbon tetrachloride clathrate. There is significant secondary bonding between the sulphur (donor) of the isothiocyanate ligand of the host and the iodines (acceptor) of the halogenated guest molecules in compounds III, IV and V. The iodoform clathrates, compounds IV and V, also show strong similarities in their packings. Particular attention has been paid to the shape and size of the cavities in which the guest molecules find themselves, in order to gain a better understanding of the nature of these clathrates. This has also shed some light on the probable cause of the disordered diiodomethane molecules in STRUCTURE III. Packing densities and volume comparisons of the [Ni(NCS)₂(4-ViPy)₂] clathrates have been carried out. Solid - state U.V/visible spectroscopy was used to obtain information on the host conformation, and thermal analysis (thermogravimatry and differential thermal analysis) was used to obtain insight into the host - guest interactions of these clathrates.

Thesis (Ph. D.)--Dept. of Physical and Inorganic Chemistry, University of Adelaide, 1986. / Includes bibliographical references (leaf 179).

Thesis (Ph. D.)--Oregon State University, 2010. / Printout. Includes bibliographical references (leaves 157-169). Also available on the World Wide Web.

Thesis (MTech (Chemistry))--Cape Peninsula University of Technology, 2009 / The host compound 9-(4-methoxyphenyl)-9H-xanthen-9-01 (AI) forms inclusion compounds with the solid guests l -naphthylamine (NAPH), 8-hydroxyquinoline (HQ). acridine (ACRI), 1,4 - diazabicyclo[2.2.2]octane (DABCO) and a liquid guest benzaldehyde (BENZAL). All four structures AI·YzNAPH, AI· Y,HQ AI·ACRI and AI ·Y,DABCO were successfully solved in the triclinic space group P I . The structure of AI·Y,BENZAL was successfully solved in the monocl inic space group P2dn . Similar packin g motifs arise for the NAPH and HQ inclusion compounds where the main interaction is of the fonm (Host)-OH····O-(Host). Both the DABCO and the ACRI guests hydrogen bond to the host molecule. The host: guest ratios for A I·ACRI. AI· Y,NAPH. A I· Y,DABCO and A I· YzHQ were found using nuclear magnetic resonance (NMR) spectroscopy. The host:guest ratio for AI·YzBENZAL was found using thenmogravimetric analysis. Enthalpy changes of the inclusion compounds were monitored using differential scanning calorimetry (DSC). Kinetics of desolvation for AI·Y,BENZAL were conducted using a non - isothenmal method where we have obtained an activation energy range of 74 k J morl - 86 k J mor' . The solid - solid reaction kinetics for A I·Y,NAPH, A I· Y,HQ, AI·ACRI and AI ·Y,DABCO were determined at room temperature using powder X-ray diffraction (PXRD).

by Qi Li. / Thesis (Ph.D.)--Chinese University of Hong Kong, 1996. / Includes bibliographical references (leaves 192-199). / Acknowledgment --- p.i / Abstract --- p.ii / Table of Contents --- p.iii / Index of Componds --- p.iv / List of Tables --- p.v / List of Figures --- p.vi / Chapter 1. --- Introduction --- p.1 / Chapter 1.1. --- General Survey of Inclusion Chemistry --- p.1 / Chapter 1.2. --- The Importance of Hydrogen Bonds --- p.5 / Chapter 1.3. --- "Classical Inclusion Compounds of Urea, Thiourea and Selenourea" --- p.8 / Chapter 1.4. --- Research Strategy --- p.12 / Chapter 2. --- Description of Crystal Structures --- p.16 / Chapter 2.1. --- Urea-Anion Inclusion Compounds --- p.16 / Chapter 2.1.1. --- Halide complexes --- p.18 / Chapter 2.1.2. --- Bicarbonate complexes --- p.30 / Chapter 2.1.3. --- Allophanate complexes --- p.36 / Chapter 2.1.4. --- Borate and pentaborate complexes --- p.44 / Chapter 2.1.5. --- Complex featuring both host-host and host-guest hydrogen bonding --- p.60 / Chapter 2.1.6. --- Tetraethylammonium and phosphonium chloride complexes --- p.65 / Chapter 2.2. --- Thiourea-Anion Inclusion Compounds --- p.71 / Chapter 2.2.1. --- Halide Complexes --- p.73 / Chapter 2.2.2. --- Bicarbonate Complexes --- p.76 / Chapter 2.2.3. --- Nitrate Complexes --- p.87 / Chapter 2.2.4. --- Formate Complexes --- p.101 / Chapter 2.2.5. --- Acetate Complexes --- p.113 / Chapter 2.2.6. --- Oxalate and Fumarate Complexes --- p.127 / Chapter 2.2.7. --- Unsymmetrical quaternary ammonium ions as guests --- p.138 / Chapter 2.3. --- Selenourea-Anion Inclusion Compounds --- p.152 / Chapter 3. --- Summary and Discussion --- p.161 / Chapter 3.1. --- Structural Features and Relationships --- p.161 / Chapter 3.2. --- Hydrogen Bonding in Urea/Thiourea/Selenourea-Anion Inclusion Compounds --- p.164 / Chapter 3.3. --- Linkage Modes of Urea and Thiourea Molecules --- p.168 / Chapter 3.4. --- Comolecular Aggregates of Urea and Other Host Components --- p.173 / Chapter 3.5. --- Comolecular Aggregates of Thiourea and Other Host Components --- p.175 / Chapter 4. --- Experimental --- p.177 / Chapter 4.1. --- Preparation --- p.177 / Chapter 4.2. --- Crystallography --- p.182 / Chapter 5. --- References --- p.192 / Appendix A: Tables of Atomic coordinates and thermal parameters --- p.200 / Appendix B: Publication Based on Results Reported in This Thesis --- p.243

Investigation on a series of hydrogen-bonded networks constructed with N-heteroaryl acids is described in Section 3.4. In this section, we focused on the connection modes within the heteroaryl dimer. The study of co-crystals and inclusion compounds based on 2-thiobarbituric acid (TBA) or trithiocyanuric acid (TCA) indicated that the dimer of TBA is present in all three crystals in the forms of ribbon, tetramer or separated dimer. In the case of 5-nitrobarbiturate, its dimer occurs in two ammonium salts and in three of its four thiourea complexes, but is absent in all three urea complexes. / Self-assembly of two-dimensional hydrogen-bonded honeycomb grids exhibiting the rosette motif has been conducted with the guanidinium cation and various anions as the building blocks, tetraalkylammonium ions of suitable bulk being employed as interlayer templates. It is noteworthy that the rosette layer constructed from three different trigonal-planar molecular components has been achieved. In addition, deviating from conventional topological design, the generation of new rosette layers, albeit highly distorted, has also been accomplished with 1,2-dithiosquarate and the dianionic form of 1,1'-biphenyl-2,2',6,6'-tetracarboxylate that do not conform to C3-symmetry. Although threefold molecular symmetry is regarded as a sacrosanct requirement for molecular building blocks in the construction of hydrogen-bonded rosette motif, this study shows that rosette motifs can be generated even if one of the building blocks does not have inherent threefold symmetry. / Study of compounds containing the deprotonated forms of Kemp's triacid (H3KTA) has revealed the chair or twist-boat conformation in six crystal structures. X-ray structural analysis showed that [C(NH2) 3+] · [C6H6(CH3) 3(COOH)2(COO-)] (2.2.2) exhibits a corrugated layer structure which mimics the rosette motif constructed from the guanidinium ion and the hydrogen carbonate dimer. The tricarboxylate form of Kemp's triacid KTA3- in 3[C(NH2) 3+] · [C6H6(CH3) 3(COO-)3] (2.2.4) registers a record number of eighteen acceptor hydrogen bonds involving the convergent N--H donor sites from nine guanidinium ions. The crystal structure of 3[(C2H5)4N+] · 20[C(NH 2)3+] · 11[C6H6(CH 3)3(COOH) (COO-)2] · [C6H6(CH3)3(COOH)2(COO -)]·17H2O (2.2.3) features a hydrogen-bonded aggregate with a centrosymmetric pseudo-octahedral arrangement of H2KTA- anions surrounding an inner core composed of eight guanidinium ions. The unusual twist-boat conformation of KTA3- is found in [(CH3)4N +] · 2[C(NH2)3+] · [C6H6(CH3)3(COO- )3] · 2H2O (2.2.6), which is stabilized by the co-existence of guanidinium and tetramethylammonium cations. / Systematic investigation on hydrogen-bonded supramolecular assembly using aromatic carboxylic acids bearing linear or bent skeletons with urea/guanidinium resulted in the formation of mainly R228 and R126 synthon motifs. In addition, isostructures were also constructed by varying the length of the linker between two carboxylate groups, as in naphthalene-2,6-dicarboxylate (2.3.2) and biphenyl dicarboxylate (2.3.3). / This thesis reports a systematic investigation on the generation of new inclusion compounds by the combined use of urea/thiourea, guanidinium ion and various organic anions as building blocks of hydrogen-bonded host lattices and selected quaternary ammonium ion as the enclosed guests. / Various acids bearing specific functional groups have been explored as structure building components, including boric acid, Kemp's triacid, heterocyclic (thio)urea derivatives, aryl and N-heteroaryl carboxylic acids and (dithio)squaric acid. All the co-crystals and inclusion compounds built of molecular components in the afore-mentioned categories have been characterized by single-crystal X-ray analysis. As a result, the complexes exhibit a rich variety of inclusion topologies, such as networks containing isolated cages, open channels, intersecting tunnels, double-layer systems, and sandwich-like as well as wave-like layer structures. / Han, Jie. / Adviser: Thomas C. W. Mak. / Source: Dissertation Abstracts International, Volume: 71-01, Section: B, page: 0337. / Thesis (Ph.D.)--Chinese University of Hong Kong, 2009. / Includes bibliographical references (leaves 204-218). / 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 Company, [200-] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Abstracts in English and Chinese.