{"id":{"repo_id":"windsor","oai_identifier":"oai:uwindsor.scholaris.ca:20.500.14776/5960"},"canonical_url":"https://search.dev.ndltd.org/etd/windsor/oai:uwindsor.scholaris.ca:20.500.14776/5960","repository":{"repo_id":"windsor","name":"University of Windsor","base_url":"https://uwindsor.scholaris.ca/server/oai/request"},"display":{"title":"New Rotaxane Ligands with Donors on Both the Axle and Wheel","abstract":"This thesis presents the design, synthesis and characterization of [2]rotaxane, [2]pseudorotaxane and [3]rotaxane ligands and their resulting coordination to metal centers. Chapter 1 introduces the concepts of interpenetrated and interlocked molecules, molecular motion, metal-ligand interactions and metal organic rotaxane frameworks (MORFs). Chapter 2 explores the preliminary studies of the coordination ability of a model compound containing a xylene backbone with two sulphur donor atoms to a range of metal ions with various geometries. This was followed by the synthesis of a new thioether crown ether ligand and the resulting coordination of this ligand with the same metal centers studied with the model ligand. Where possible, the single crystal X-ray data for these coordination complexes was collected and has been presented. In chapter 3, this new thioether crown ether was used in the formation of [2]rotaxane ligands. Upon the addition of silver(I), the sulphur atoms of the crown ether coordinated to the metal center forming a 1D polymer strand with a zig-zag pattern. A [2]rotaxane with sulphur atoms on both the wheel and axle resulting in six donors, was synthesized and coordinated to silver(I). The result is a unique interwoven MOF architecture containing a 1D polymer strand connected to a 2D polymer sheet by the interlocked nature of the [2]rotaxane. Chapter 4 takes a look at a [2]pseudorotaxane with two sulphur atoms on the crown ether and one sulphur atom on the axle. This system has the potential to switch to a [1]rotaxane upon the addition of a metal center as both the axle and wheel coordinate to a metal center. The metal center acts as a stopper preventing the individual components from separating. Coordination of the [2]pseudorotaxane to silver(I) was observed through 1H NMR spectroscopy, but a shift in equilibrium occurs as pseudorotaxane formation becomes less favourable. Chapter 5 describes the synthesis of a [3]rotaxane and the resulting coordination of the neutral [3]rotaxane ligand to a range of metals. Coordination to the metal center does occur but in the process the [3]rotaxane becomes protonated. The final chapter summarizes the lessons learned and possible future endeavors.","abstract_html":"This thesis presents the design, synthesis and characterization of [2]rotaxane, [2]pseudorotaxane and [3]rotaxane ligands and their resulting coordination to metal centers. Chapter 1 introduces the concepts of interpenetrated and interlocked molecules, molecular motion, metal-ligand interactions and metal organic rotaxane frameworks (MORFs). Chapter 2 explores the preliminary studies of the coordination ability of a model compound containing a xylene backbone with two sulphur donor atoms to a range of metal ions with various geometries. This was followed by the synthesis of a new thioether crown ether ligand and the resulting coordination of this ligand with the same metal centers studied with the model ligand. Where possible, the single crystal X-ray data for these coordination complexes was collected and has been presented. In chapter 3, this new thioether crown ether was used in the formation of [2]rotaxane ligands. Upon the addition of silver(I), the sulphur atoms of the crown ether coordinated to the metal center forming a 1D polymer strand with a zig-zag pattern. A [2]rotaxane with sulphur atoms on both the wheel and axle resulting in six donors, was synthesized and coordinated to silver(I). The result is a unique interwoven MOF architecture containing a 1D polymer strand connected to a 2D polymer sheet by the interlocked nature of the [2]rotaxane. Chapter 4 takes a look at a [2]pseudorotaxane with two sulphur atoms on the crown ether and one sulphur atom on the axle. This system has the potential to switch to a [1]rotaxane upon the addition of a metal center as both the axle and wheel coordinate to a metal center. The metal center acts as a stopper preventing the individual components from separating. Coordination of the [2]pseudorotaxane to silver(I) was observed through 1H NMR spectroscopy, but a shift in equilibrium occurs as pseudorotaxane formation becomes less favourable. Chapter 5 describes the synthesis of a [3]rotaxane and the resulting coordination of the neutral [3]rotaxane ligand to a range of metals. Coordination to the metal center does occur but in the process the [3]rotaxane becomes protonated. The final chapter summarizes the lessons learned and possible future endeavors.","abstract_has_math":false,"creators":["Frank, Nissa Christina"],"institution":"University of Windsor","degree_name":"Ph.D.","degree_level":"Doctoral","degree_discipline":"Chemistry and Biochemistry","degree_department":null,"school":null,"contributors":[],"advisors":["Loeb, Stephen"],"committee_chairs":[],"committee_members":[],"year":2016,"date_issued":"2016-01-27","date_published":"2016-01-27","updated_at":"2026-07-27T22:04:44Z","subjects":[],"languages":["en_CA"],"rights":[],"rights_urls":["http://creativecommons.org/licenses/by-nc-nd/4.0/"],"identifier_entries":[]},"links":{"outbound_url":"https://hdl.handle.net/20.500.14776/5960","outbound_label":"Handle","outbound_source":"dc:identifier.uri"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.advisor","label":"Advisor","values":["Loeb, Stephen"]},{"key":"dc:creator","label":"Author","values":["Frank, Nissa Christina"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.accessioned","label":"Dc Date Accessioned","values":["2025-06-24 12:33"]},{"key":"dc:date.available","label":"Dc Date Available","values":["2016-03-02 8:38","2025-06-24T16:33:04Z"]},{"key":"dc:date.issued","label":"Date","values":["2016-01-27"]},{"key":"dc:type","label":"Dc Type","values":["info:eu-repo/semantics/doctoralThesis"]},{"key":"thesis:degree_discipline","label":"Discipline","values":["Chemistry and Biochemistry"]},{"key":"thesis:degree_level","label":"Degree Level","values":["Doctoral"]},{"key":"thesis:degree_name","label":"Degree Name","values":["Ph.D."]},{"key":"thesis:institution_name","label":"Thesis Institution Name","values":["University of Windsor"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language.iso","label":"Language (ISO)","values":["en_CA"]},{"key":"dc:rights","label":"Dc Rights","values":["http://creativecommons.org/licenses/by-nc-nd/4.0/"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier.uri","label":"Identifier URI","values":["https://hdl.handle.net/20.500.14776/5960"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["This thesis presents the design, synthesis and characterization of [2]rotaxane, [2]pseudorotaxane and [3]rotaxane ligands and their resulting coordination to metal centers. Chapter 1 introduces the concepts of interpenetrated and interlocked molecules, molecular motion, metal-ligand interactions and metal organic rotaxane frameworks (MORFs). Chapter 2 explores the preliminary studies of the coordination ability of a model compound containing a xylene backbone with two sulphur donor atoms to a range of metal ions with various geometries. This was followed by the synthesis of a new thioether crown ether ligand and the resulting coordination of this ligand with the same metal centers studied with the model ligand. Where possible, the single crystal X-ray data for these coordination complexes was collected and has been presented. In chapter 3, this new thioether crown ether was used in the formation of [2]rotaxane ligands. Upon the addition of silver(I), the sulphur atoms of the crown ether coordinated to the metal center forming a 1D polymer strand with a zig-zag pattern. A [2]rotaxane with sulphur atoms on both the wheel and axle resulting in six donors, was synthesized and coordinated to silver(I). The result is a unique interwoven MOF architecture containing a 1D polymer strand connected to a 2D polymer sheet by the interlocked nature of the [2]rotaxane. Chapter 4 takes a look at a [2]pseudorotaxane with two sulphur atoms on the crown ether and one sulphur atom on the axle. This system has the potential to switch to a [1]rotaxane upon the addition of a metal center as both the axle and wheel coordinate to a metal center. The metal center acts as a stopper preventing the individual components from separating. Coordination of the [2]pseudorotaxane to silver(I) was observed through 1H NMR spectroscopy, but a shift in equilibrium occurs as pseudorotaxane formation becomes less favourable. Chapter 5 describes the synthesis of a [3]rotaxane and the resulting coordination of the neutral [3]rotaxane ligand to a range of metals. Coordination to the metal center does occur but in the process the [3]rotaxane becomes protonated. The final chapter summarizes the lessons learned and possible future endeavors."]},{"key":"dc:title","label":"Title","values":["New Rotaxane Ligands with Donors on Both the Axle and Wheel"]}]}],"canonical_facts":{"dc:contributor.advisor":["Loeb, Stephen"],"dc:creator":["Frank, Nissa Christina"],"dc:date.accessioned":["2025-06-24 12:33"],"dc:date.available":["2016-03-02 8:38","2025-06-24T16:33:04Z"],"dc:date.issued":["2016-01-27"],"dc:description.abstract":["This thesis presents the design, synthesis and characterization of [2]rotaxane, [2]pseudorotaxane and [3]rotaxane ligands and their resulting coordination to metal centers. Chapter 1 introduces the concepts of interpenetrated and interlocked molecules, molecular motion, metal-ligand interactions and metal organic rotaxane frameworks (MORFs). Chapter 2 explores the preliminary studies of the coordination ability of a model compound containing a xylene backbone with two sulphur donor atoms to a range of metal ions with various geometries. This was followed by the synthesis of a new thioether crown ether ligand and the resulting coordination of this ligand with the same metal centers studied with the model ligand. Where possible, the single crystal X-ray data for these coordination complexes was collected and has been presented. In chapter 3, this new thioether crown ether was used in the formation of [2]rotaxane ligands. Upon the addition of silver(I), the sulphur atoms of the crown ether coordinated to the metal center forming a 1D polymer strand with a zig-zag pattern. A [2]rotaxane with sulphur atoms on both the wheel and axle resulting in six donors, was synthesized and coordinated to silver(I). The result is a unique interwoven MOF architecture containing a 1D polymer strand connected to a 2D polymer sheet by the interlocked nature of the [2]rotaxane. Chapter 4 takes a look at a [2]pseudorotaxane with two sulphur atoms on the crown ether and one sulphur atom on the axle. This system has the potential to switch to a [1]rotaxane upon the addition of a metal center as both the axle and wheel coordinate to a metal center. The metal center acts as a stopper preventing the individual components from separating. Coordination of the [2]pseudorotaxane to silver(I) was observed through 1H NMR spectroscopy, but a shift in equilibrium occurs as pseudorotaxane formation becomes less favourable. Chapter 5 describes the synthesis of a [3]rotaxane and the resulting coordination of the neutral [3]rotaxane ligand to a range of metals. Coordination to the metal center does occur but in the process the [3]rotaxane becomes protonated. The final chapter summarizes the lessons learned and possible future endeavors."],"dc:identifier.uri":["https://hdl.handle.net/20.500.14776/5960"],"dc:language.iso":["en_CA"],"dc:rights":["http://creativecommons.org/licenses/by-nc-nd/4.0/"],"dc:title":["New Rotaxane Ligands with Donors on Both the Axle and Wheel"],"dc:type":["info:eu-repo/semantics/doctoralThesis"],"thesis:degree_discipline":["Chemistry and Biochemistry"],"thesis:degree_level":["Doctoral"],"thesis:degree_name":["Ph.D."],"thesis:institution_name":["University of Windsor"]},"updated_at":"2026-07-27T22:04:44Z"}