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The structural analysis of imidazole-functionalised metallocycles
Thesis (PhD)--Stellenbosch University, 2012.
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| Format: | Thesis |
| Language: | en_ZA |
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Stellenbosch : Stellenbosch University
2012
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| _version_ | 1867614011995979777 |
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| access_status_str | Open Access |
| author | Loots, Leigh-Anne |
| author2 | Barbour, Leonard J. |
| author_browse | Barbour, Leonard J. Loots, Leigh-Anne |
| author_facet | Barbour, Leonard J. Loots, Leigh-Anne |
| author_sort | Loots, Leigh-Anne |
| collection | Thesis |
| dc_rights_str_mv | Stellenbosch University |
| description | Thesis (PhD)--Stellenbosch University, 2012. |
| format | Thesis |
| id | oai:scholar.sun.ac.za:10019.1/71952 |
| institution | Stellenbosch University (South Africa) |
| language | en_ZA |
| last_indexed | 2026-06-10T12:45:16.097Z |
| license_str | Other — see source repository |
| provenance_str_mv | Harvested via OAI-PMH from SUNScholar — Stellenbosch University Repository |
| publishDate | 2012 |
| publishDateRange | 2012 |
| publishDateSort | 2012 |
| publisher | Stellenbosch : Stellenbosch University |
| publisherStr | Stellenbosch : Stellenbosch University |
| record_format | dspace |
| source_str | SUNScholar — Stellenbosch University Repository |
| spelling | oai:scholar.sun.ac.za:10019.1/71952 The structural analysis of imidazole-functionalised metallocycles Loots, Leigh-Anne Barbour, Leonard J. Stellenbosch University. Faculty of Science. Dept. of Chemistry and Polymer Science. Metallocycles Supramolecular Crystalline polymers Thermal gravimetric analysis Thesis (PhD)--Stellenbosch University, 2012. ENGLISH ABSTRACT: The primary objective of this study was to synthesise novel metallocyclic compounds and analyse their crystal structures. To this end seven novel imidazole-functionalised ligands were synthesised and reacted with a variety of transition-metal halide salts. In addition to this study a new, simple, yet robust methodology for the analysis of π···π packing motifs in aromatic molecules is described. Seventeen homeotypic metallocyclic compounds were obtained with a ligand containing a dimethoxyphenyl spacer between imidazole functionalities. These compounds form reliably from a number of solvent systems involving acetonitrile and they all include acetonitrile molecules as part of their host assembly. In each case a second guest molecule is enclosed within the walls of the metallocycles. These compounds are compared by means of thermal analysis, calculated powder X-ray diffraction patterns as well as crystal packing similarity calculations. Metallocycles prepared from a phenanthrene-based ligand form an unprecedented infinite π···π stack, which induces the assembly of an infinite catenane. This catenane forms concomitantly with its topological isomer, which consists of unlinked metallocycles. The intermolecular interactions responsible for the two topologically unique structures were investigated. Finally, a further twelve metallocycles were prepared from four novel imidazolefunctionalised ligands and their structures were analysed for any similarities and/or differences. A few of these crystals showed the release of solvent guest molecules as singlecrystal to single-crystal transformations. AFRIKAANSE OPSOMMING: Die primêre doel van hierdie studie was om nuwe metallosiklieseverbindings te sintetiseer en hul kristalstrukture te ontleed. Vir hierdie doel is sewe nuwe imidasool-gefunksionaliseerde ligande gesintetiseer en gereageer met 'n verskeidenheid van oorgangsmetaalhaliedsoute. In hierdie studie word 'n nuwe, eenvoudige, maar robuuste metode vir die ontleding van π···π verpakkingmotiewe in aromatise molekules beskryf. Sewentien homeotipiese metallosiklieseverbindings is verkry met 'n ligand met 'n dimetoksifeniel spasieerder tussen imidasool funksionaliteite. Hierdie verbindings vorm op betroubare wyse vanuit 'n aantal oplosmiddelsisteme wat asetonitriel behels en almal sluit asetonitriel molekules as deel van hul gasheer samestelling in. In elke geval is 'n tweede gasmolekule ingesluit binne die mure van die metallosiklieseverbindings. Hierdie verbindings is deur middel van termiese analise, berekende poeier X-straaldiffraksie patrone, sowel as kristalverpakking gelykvormigheidsberekeninge vergelyk. Metallosiklieseverbindings wat voorberei is vanaf 'n phenanthrene-gebaseerde ligand, vorm 'n uitsonderlike oneindige π···π verpakking, wat die samestelling van 'n oneindige katenaan tot gevolg het. Hierdie katenaan vorm saam met sy topologiese isomeer, wat bestaan uit ongekoppelde metallosiklieseverbindings. Die intermolekulêre interaksies wat verantwoordelik is vir die twee topologies unieke strukture word ondersoek. Ten slotte, was 'n verdere twaalf metallosiklieseverbindings uit vier voorheen onbekende imidasool-gefunksionaliseerde ligande voorberei en hul strukture is vir enige ooreenkomste en/of verskille ontleed. 'n Paar van hierdie kristalle ondergaan die vrystelling van die oplosmiddelmolekules as 'n enkel-kristal na enkel-kristal omsetting. Doctoral 2012-07-02T12:18:24Z 2012-12-12T08:17:31Z 2012-07-02T12:18:24Z 2012-12-12T08:17:31Z 2012-12 Thesis http://hdl.handle.net/10019.1/71952 en_ZA Stellenbosch University 208 pages application/pdf application/pdf Stellenbosch : Stellenbosch University |
| spellingShingle | Metallocycles Supramolecular Crystalline polymers Thermal gravimetric analysis Loots, Leigh-Anne The structural analysis of imidazole-functionalised metallocycles |
| title | The structural analysis of imidazole-functionalised metallocycles |
| title_full | The structural analysis of imidazole-functionalised metallocycles |
| title_fullStr | The structural analysis of imidazole-functionalised metallocycles |
| title_full_unstemmed | The structural analysis of imidazole-functionalised metallocycles |
| title_short | The structural analysis of imidazole-functionalised metallocycles |
| title_sort | structural analysis of imidazole functionalised metallocycles |
| topic | Metallocycles Supramolecular Crystalline polymers Thermal gravimetric analysis |
| url | http://hdl.handle.net/10019.1/71952 |
| work_keys_str_mv | AT lootsleighanne thestructuralanalysisofimidazolefunctionalisedmetallocycles AT lootsleighanne structuralanalysisofimidazolefunctionalisedmetallocycles |