{"id":{"repo_id":"windsor","oai_identifier":"oai:uwindsor.scholaris.ca:20.500.14776/2190"},"canonical_url":"https://search.dev.ndltd.org/etd/windsor/oai:uwindsor.scholaris.ca:20.500.14776/2190","repository":{"repo_id":"windsor","name":"University of Windsor","base_url":"https://uwindsor.scholaris.ca/server/oai/request"},"display":{"title":"New Liquid Crystalline [2]Rotaxanes","abstract":"This thesis presents design, synthesis and characterization of a range of new liquid crystalline interlocked molecules and to study structure-property relationships between rotaxane design and mesomorphism. Chapter 1 introduces concepts of supramolecular chemistry and liquid crystals and cooperative effect between [2]rotaxane and liquid crystals towards functional molecular machines. In Chapter 2, a systematic approach to introduce liquid crystallinity into the 1,2-bis(pyridinium)ethane/DB24C8 motif is described. The chapter begins with synthesis and purification of dumbbells (without macrocycle) and [2]rotaxanes (with macrocycle) substituted with purely aliphatic extended 3,5-disubstituted stoppers with increasing alkyl chain length. Chapter continues with phase characterization and structure-property relationships between dumbbells and rotaxanes. The dodecane chain was sufficiently fluid to induce smectic mesomorphism in both the dumbbell and [2]rotaxane, with [2]rotaxane forming SmA phase by POM and XRD analysis. Chapter 3 presents an extension to Chapter 2 with the addition of longer straight chain and branching aliphatic chains to our 1,2-bis(pyridinium)ethane/DB24C8 rotaxane motif to study structure-property relationships and phase characteristics. The ability of the side-chain to self-organized showed large differences in phase behaviour. The pentadecane straight chain extended [2]rotaxane exhibited a unidentified mesophase, the hexadecane straight chain [2]rotaxane showed SmA mesomorphism, the branched hexadecane and the hyperbranched [2]rotaxanes both showed lamellar soft crystal phases. Chapter 4 describes the effect of applying groups typical for low molecular weight LCs (siloxanes) to our 1,2-bis(pyridinium)ethane/DB24C8 motif and a modified rotaxane design based on a bis(oxymethylbenzylpyridinium)ethane/DB24C8 motif. The structure-property relations between both systems, and in comparison with the dodecane chain substituted systems, are presented. The new design revealed SmC mesophases for both the dodecane and siloxane substituted [2]rotaxanes. Chapter 5 focuses on the introduction of chirality into the siloxane substituted [2]rotaxane with SmC mesomorphism presented in Chapter 4. Chirality was introduced via a chiral anion as well as incorporation of a chiral crown. Observations to changes in the superstructure from the incorporation of chirality is addressed. The chiral anion exchanged [2]rotaxane showed SmC* mesomorphism and the chiral crown [2]rotaxane showed SmX* mesomorphism. Chapter 6 presents the design and synthesis of a molecular shuttle based upon the structure-property relations determined from the previous chapters.","abstract_html":"This thesis presents design, synthesis and characterization of a range of new liquid crystalline interlocked molecules and to study structure-property relationships between rotaxane design and mesomorphism. Chapter 1 introduces concepts of supramolecular chemistry and liquid crystals and cooperative effect between [2]rotaxane and liquid crystals towards functional molecular machines. In Chapter 2, a systematic approach to introduce liquid crystallinity into the 1,2-bis(pyridinium)ethane/DB24C8 motif is described. The chapter begins with synthesis and purification of dumbbells (without macrocycle) and [2]rotaxanes (with macrocycle) substituted with purely aliphatic extended 3,5-disubstituted stoppers with increasing alkyl chain length. Chapter continues with phase characterization and structure-property relationships between dumbbells and rotaxanes. The dodecane chain was sufficiently fluid to induce smectic mesomorphism in both the dumbbell and [2]rotaxane, with [2]rotaxane forming SmA phase by POM and XRD analysis. Chapter 3 presents an extension to Chapter 2 with the addition of longer straight chain and branching aliphatic chains to our 1,2-bis(pyridinium)ethane/DB24C8 rotaxane motif to study structure-property relationships and phase characteristics. The ability of the side-chain to self-organized showed large differences in phase behaviour. The pentadecane straight chain extended [2]rotaxane exhibited a unidentified mesophase, the hexadecane straight chain [2]rotaxane showed SmA mesomorphism, the branched hexadecane and the hyperbranched [2]rotaxanes both showed lamellar soft crystal phases. Chapter 4 describes the effect of applying groups typical for low molecular weight LCs (siloxanes) to our 1,2-bis(pyridinium)ethane/DB24C8 motif and a modified rotaxane design based on a bis(oxymethylbenzylpyridinium)ethane/DB24C8 motif. The structure-property relations between both systems, and in comparison with the dodecane chain substituted systems, are presented. The new design revealed SmC mesophases for both the dodecane and siloxane substituted [2]rotaxanes. Chapter 5 focuses on the introduction of chirality into the siloxane substituted [2]rotaxane with SmC mesomorphism presented in Chapter 4. Chirality was introduced via a chiral anion as well as incorporation of a chiral crown. Observations to changes in the superstructure from the incorporation of chirality is addressed. The chiral anion exchanged [2]rotaxane showed SmC* mesomorphism and the chiral crown [2]rotaxane showed SmX* mesomorphism. Chapter 6 presents the design and synthesis of a molecular shuttle based upon the structure-property relations determined from the previous chapters.","abstract_has_math":false,"creators":["Suhan, Natalie"],"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 J.(Chemistry and Biochemistry)"],"committee_chairs":[],"committee_members":[],"year":2009,"date_issued":"2009-01-01","date_published":"2009-01-01","updated_at":"2026-07-27T22:04:52Z","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/20.500.14776/2190","outbound_label":"Handle","outbound_source":"dc:identifier.uri"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.advisor","label":"Advisor","values":["Loeb, Stephen J.(Chemistry and Biochemistry)"]},{"key":"dc:creator","label":"Author","values":["Suhan, Natalie"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.accessioned","label":"Dc Date Accessioned","values":["2025-06-20 10:13"]},{"key":"dc:date.available","label":"Dc Date Available","values":["2012-10-26 7:20","2025-06-20T14:13:05Z"]},{"key":"dc:date.issued","label":"Date","values":["2009-01-01"]},{"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/20.500.14776/2190"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["This thesis presents design, synthesis and characterization of a range of new liquid crystalline interlocked molecules and to study structure-property relationships between rotaxane design and mesomorphism. Chapter 1 introduces concepts of supramolecular chemistry and liquid crystals and cooperative effect between [2]rotaxane and liquid crystals towards functional molecular machines. In Chapter 2, a systematic approach to introduce liquid crystallinity into the 1,2-bis(pyridinium)ethane/DB24C8 motif is described. The chapter begins with synthesis and purification of dumbbells (without macrocycle) and [2]rotaxanes (with macrocycle) substituted with purely aliphatic extended 3,5-disubstituted stoppers with increasing alkyl chain length. Chapter continues with phase characterization and structure-property relationships between dumbbells and rotaxanes. The dodecane chain was sufficiently fluid to induce smectic mesomorphism in both the dumbbell and [2]rotaxane, with [2]rotaxane forming SmA phase by POM and XRD analysis. Chapter 3 presents an extension to Chapter 2 with the addition of longer straight chain and branching aliphatic chains to our 1,2-bis(pyridinium)ethane/DB24C8 rotaxane motif to study structure-property relationships and phase characteristics. The ability of the side-chain to self-organized showed large differences in phase behaviour. The pentadecane straight chain extended [2]rotaxane exhibited a unidentified mesophase, the hexadecane straight chain [2]rotaxane showed SmA mesomorphism, the branched hexadecane and the hyperbranched [2]rotaxanes both showed lamellar soft crystal phases. Chapter 4 describes the effect of applying groups typical for low molecular weight LCs (siloxanes) to our 1,2-bis(pyridinium)ethane/DB24C8 motif and a modified rotaxane design based on a bis(oxymethylbenzylpyridinium)ethane/DB24C8 motif. The structure-property relations between both systems, and in comparison with the dodecane chain substituted systems, are presented. The new design revealed SmC mesophases for both the dodecane and siloxane substituted [2]rotaxanes. Chapter 5 focuses on the introduction of chirality into the siloxane substituted [2]rotaxane with SmC mesomorphism presented in Chapter 4. Chirality was introduced via a chiral anion as well as incorporation of a chiral crown. Observations to changes in the superstructure from the incorporation of chirality is addressed. The chiral anion exchanged [2]rotaxane showed SmC* mesomorphism and the chiral crown [2]rotaxane showed SmX* mesomorphism. Chapter 6 presents the design and synthesis of a molecular shuttle based upon the structure-property relations determined from the previous chapters."]},{"key":"dc:title","label":"Title","values":["New Liquid Crystalline [2]Rotaxanes"]}]}],"canonical_facts":{"dc:contributor.advisor":["Loeb, Stephen J.(Chemistry and Biochemistry)"],"dc:creator":["Suhan, Natalie"],"dc:date.accessioned":["2025-06-20 10:13"],"dc:date.available":["2012-10-26 7:20","2025-06-20T14:13:05Z"],"dc:date.issued":["2009-01-01"],"dc:description.abstract":["This thesis presents design, synthesis and characterization of a range of new liquid crystalline interlocked molecules and to study structure-property relationships between rotaxane design and mesomorphism. Chapter 1 introduces concepts of supramolecular chemistry and liquid crystals and cooperative effect between [2]rotaxane and liquid crystals towards functional molecular machines. In Chapter 2, a systematic approach to introduce liquid crystallinity into the 1,2-bis(pyridinium)ethane/DB24C8 motif is described. The chapter begins with synthesis and purification of dumbbells (without macrocycle) and [2]rotaxanes (with macrocycle) substituted with purely aliphatic extended 3,5-disubstituted stoppers with increasing alkyl chain length. Chapter continues with phase characterization and structure-property relationships between dumbbells and rotaxanes. The dodecane chain was sufficiently fluid to induce smectic mesomorphism in both the dumbbell and [2]rotaxane, with [2]rotaxane forming SmA phase by POM and XRD analysis. Chapter 3 presents an extension to Chapter 2 with the addition of longer straight chain and branching aliphatic chains to our 1,2-bis(pyridinium)ethane/DB24C8 rotaxane motif to study structure-property relationships and phase characteristics. The ability of the side-chain to self-organized showed large differences in phase behaviour. The pentadecane straight chain extended [2]rotaxane exhibited a unidentified mesophase, the hexadecane straight chain [2]rotaxane showed SmA mesomorphism, the branched hexadecane and the hyperbranched [2]rotaxanes both showed lamellar soft crystal phases. Chapter 4 describes the effect of applying groups typical for low molecular weight LCs (siloxanes) to our 1,2-bis(pyridinium)ethane/DB24C8 motif and a modified rotaxane design based on a bis(oxymethylbenzylpyridinium)ethane/DB24C8 motif. The structure-property relations between both systems, and in comparison with the dodecane chain substituted systems, are presented. The new design revealed SmC mesophases for both the dodecane and siloxane substituted [2]rotaxanes. Chapter 5 focuses on the introduction of chirality into the siloxane substituted [2]rotaxane with SmC mesomorphism presented in Chapter 4. Chirality was introduced via a chiral anion as well as incorporation of a chiral crown. Observations to changes in the superstructure from the incorporation of chirality is addressed. The chiral anion exchanged [2]rotaxane showed SmC* mesomorphism and the chiral crown [2]rotaxane showed SmX* mesomorphism. Chapter 6 presents the design and synthesis of a molecular shuttle based upon the structure-property relations determined from the previous chapters."],"dc:identifier.uri":["https://hdl.handle.net/20.500.14776/2190"],"dc:language.iso":["en_CA"],"dc:rights":["http://creativecommons.org/licenses/by-nc-nd/4.0/"],"dc:title":["New Liquid Crystalline [2]Rotaxanes"],"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":"2026-07-27T22:04:52Z"}