Browsing by Author "Wahl, Helene"
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- ItemDevelopment of novel supramolecular framework materials based on organic salts(Stellenbosch : Stellenbosch University, 2014-12) Wahl, Helene; Le Roex, Tanya; Haynes, Delia A.; Stellenbosch University. Faculty of Science. Dept. of Chemistry and Polymer Science.ENGLISH ABSTRACT: The aim of the work presented in this thesis was to design ionic organic framework materials based on carboxylate salts with the intention of engineering interesting properties, such as porosity, into these framework materials. The first section focuses on the characterisation and porosity studies of an ionic framework material, 3,4-lutidinium pamoate hemihydrate, with THF-filled channels in the solid state. It was shown that this framework is able to exchange the THF in the channels for a wide variety of compounds, with many of these exchanges occurring in a single-crystal to single-crystal fashion. Competition experiments conducted with the framework, both by immersing crystals of the framework in solvent mixtures, as well as by exposing crystals of the framework to mixtures of solvent vapours, indicated that it is able to selectively exchange for one guest over another. The kinetics of exchange of this framework were studied, and it was possible to identify a kinetic model describing this process. A second novel framework-type material, 4-phenylpyridinium pamoate, was identified during the course of this study, as well as five isostructural frameworks containing different guest molecules. In this case the framework consists of discrete units that close-pack in such a way that guest molecules are included in constricted cavities in the solid state. Although this framework-type material is not porous, it is thermally quite stable and also highly selective. It is able to selectively encapsulate 1,4-dioxane when crystallised from various solvent combinations including 1,4-dioxane. In addition, eight novel structures with pamoic acid in combination with various pyridyl derivatives were obtained. A third novel framework material was obtained with N,N'-bis(glycinyl)pyromellitic diimide in which, due to the extended hydrogen-bonded network formed between the constituents of the framework, DMF molecules are aligned in channels. It was found that this framework material can also be formed by mechanochemical synthesis, and investigation of the thermal behaviour of this framework showed that it has the potential to be porous, since the framework appears to remain intact after desolvation. Furthermore, six novel structures with N,N'- bis(glycinyl)pyromellitic diimide in combination with various N-heterocycles were obtained. All structures obtained in this study were also further analysed to determine whether there are particular structural features that are required for framework formation. Insights gained from these investigations, in terms of degree of ionisation of the anion, packing arrangements and hydrogen bonding patterns as well as the molecular shape of the components are discussed.
- ItemInvestigation into co-crystal formation with cyclophosphazenes(Stellenbosch : Stellenbosch University, 2012-03) Wahl, Helene; Haynes, Delia A.; Le Roex, Tanya; Stellenbosch University. Faculty of Science. Dept. of Chemistry and Polymer Science.ENGLISH ABSTRACT: This study aimed to combine the principles of crystal engineering with the properties of cyclotriphosphazene derivatives to construct supramolecular assemblies in the solid state. The ease with which the chloro substituents on cyclotriphosphazenes can be replaced makes them ideal candidates for this study. The substituents were chosen for their ability to form either hydrogen bonding interactions or halogen bonding interactions in the solid state. The cyclotriphosphazene derivatives were co-crystallised with various small organic molecules with complementary functional groups, as well as with other cyclophosphazene derivatives. The aim was to form co-crystals or solvates with these cyclophosphazene derivatives as co-crystals contain a wealth of information regarding the forces governing the aggregation of molecules in the solid state. Cyclotriphosphazenes, with their array of substituents, could broaden the range of potential interactions governing crystalline assembly. Fifteen cyclotriphosphazene derivatives were synthesised and characterised in this study. The novel crystal structures of two cyclotriphosphazene derivatives have been elucidated by single crystal X-ray diffraction. These are 2,2-bis(4-formylphenoxy)-4,4,6,6-bis[spiro(2',2"-dioxy-1',1"-biphenylyl)]cyclotriphosphazene and hexakis(4-cyano-phenoxy)cyclotriphosphazene. In the course of this study two novel polymorphs of hexakis(4-fluorophenoxy)cyclotri-phosphazene were identified and studied. The novel triclinic form undergoes an irreversible transformation to the previously reported monoclinic phase at high temperatures. The reported monoclinic phase, however, transforms to a monoclinic C phase in a single-crystal to single-crystal fashion. It is also suspected that this phase transformation is in fact reversible on cooling of the crystal to temperatures below -45 °C. One novel co-crystal structure of hexakis(4-pyridyloxy)cyclotriphosphazene with terephthalic acid was identified and characterised. However, analysis of the Cambridge Structural Database indicates that co-crystal formation with cyclophosphazenes is not a commonly occurring phenomenon. This leads to the conclusion that cyclotriphosphazenes can be used in crystal engineering as supramolecular building blocks, but their shape and size tend to inhibit the formation of co-crystals. Therefore co-crystal formers have to be chosen with great care.
- ItemLack of co-crystal formation with cyclotriphosphazenes : a cautionary tale(South African Chemical Institute, 2016) Wahl, Helene; Haynes, Delia A.; Le Roex, TanyaENGLISH ABSTRACT: The attempted formation of co-crystals with a series of cyclotriphosphazene derivatives has been investigated. Despite numerous attempts, only one co-crystal was obtained. The crystal structure of this material, [hexakis(4-pyridyloxy)-cyclotriphosphazene][ terephthalic acid]2.5, is presented here. The crystal structures of 2,2-bis(4-formylphenoxy)-4,4,6,6-bis[spiro(2’,2”-dioxy- 1’,1”-biphenylyl]cyclo-triphosphazene and hexakis(4-cyanophenoxy)cyclotriphosphazene are also reported for the first time. The extremely low rate of co-crystal occurrence in these materials cannot be explained, despite the consideration of several possibilities. This serves as a cautionary tale – co-crystal formation is not necessarily straightforward.