{"id":{"repo_id":"brock","oai_identifier":"oai:brocku.scholaris.ca:10464/9502"},"canonical_url":"https://search.dev.ndltd.org/etd/brock/oai:brocku.scholaris.ca:10464/9502","repository":{"repo_id":"brock","name":"Brock University","base_url":"https://brocku.scholaris.ca/server/oai/request"},"display":{"title":"Polynuclear 3d/4f-Metal Complexes as Molecular Magnetic Refrigerants and Single-Molecule Magnets","abstract":"The use of two different chelating/bridging ligands, naphthalene-2,3-diol (ndH2) and acenaphthenequinone dioxime (acndH2), in heterometallic 3d/4f-metal cluster chemistry has yielded two new families of polynuclear CuII/LnIII clusters. These complexes were found to exhibit interesting magnetic properties, specifically single-molecule magnetism and the magnetocaloric effect. In this thesis, Chapter 1 lays the foundation for the research presented within. This section covers the fundamentals of polynuclear metal complexes, molecular magnetism, and the magnetocaloric effect, as well as the approaches used for the synthesis of new polynuclear metal complexes and the choice of ligands. Chapters 2 and 3 report the results of the current thesis. In Chapter 2, the synthesis and characterization of a family of {Cu4Ln} complexes (LnIII = GdIII (1), TbIII (2), DyIII (3)), employing the ligand ndH2 is presented. The complexes join a handful of previously reported {Cu4Ln} clusters, however, the family reported in this thesis are the first ‘propeller’-like clusters that exhibit single-molecule magnetism and magnetic refrigeration properties. In Chapter 3, a family of {Cu6Ln2}n chains (LnIII = GdIII (4), TbIII (5), DyIII (6)) obtained through the employment of ligand acndH2 is presented. This family of 1D-chains is a novel motif that has not been previously reported in the literature, with only a few discrete {Cu6Ln2} 0D-clusters having been previously reported. The complexes were magnetically characterized, with 4 and 5 exhibiting ferromagnetic exchange interactions while 6 revealed a more complex magnetic behaviour with both ferromagnetic and antiferromagnetic interactions dominating at different temperature regimes. Furthermore, 5 was found to behave as a single-molecule magnet and 4 was shown to act as a molecular magnetic refrigerant.","abstract_html":"The use of two different chelating/bridging ligands, naphthalene-2,3-diol (ndH2) and acenaphthenequinone dioxime (acndH2), in heterometallic 3d/4f-metal cluster chemistry has yielded two new families of polynuclear CuII/LnIII clusters. These complexes were found to exhibit interesting magnetic properties, specifically single-molecule magnetism and the magnetocaloric effect. In this thesis, Chapter 1 lays the foundation for the research presented within. This section covers the fundamentals of polynuclear metal complexes, molecular magnetism, and the magnetocaloric effect, as well as the approaches used for the synthesis of new polynuclear metal complexes and the choice of ligands. Chapters 2 and 3 report the results of the current thesis. In Chapter 2, the synthesis and characterization of a family of {Cu4Ln} complexes (LnIII = GdIII (1), TbIII (2), DyIII (3)), employing the ligand ndH2 is presented. The complexes join a handful of previously reported {Cu4Ln} clusters, however, the family reported in this thesis are the first ‘propeller’-like clusters that exhibit single-molecule magnetism and magnetic refrigeration properties. In Chapter 3, a family of {Cu6Ln2}n chains (LnIII = GdIII (4), TbIII (5), DyIII (6)) obtained through the employment of ligand acndH2 is presented. This family of 1D-chains is a novel motif that has not been previously reported in the literature, with only a few discrete {Cu6Ln2} 0D-clusters having been previously reported. The complexes were magnetically characterized, with 4 and 5 exhibiting ferromagnetic exchange interactions while 6 revealed a more complex magnetic behaviour with both ferromagnetic and antiferromagnetic interactions dominating at different temperature regimes. Furthermore, 5 was found to behave as a single-molecule magnet and 4 was shown to act as a molecular magnetic refrigerant.","abstract_has_math":false,"creators":["Richardson, Paul"],"institution":"Brock University","degree_name":"M.Sc. Chemistry","degree_level":"Masters","degree_discipline":"Faculty of Mathematics and Science","degree_department":"Department of Chemistry","school":null,"contributors":[],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2016,"date_issued":"2016-07-14T19:14:14Z","date_published":"2016-07-14T19:14:14Z","updated_at":"2026-07-24T01:22:58Z","subjects":["polynuclear 3d/4f-metal clusters","molecular magnetic refrigerants","single-molecule magnets","dioximes","diols"],"languages":["eng"],"rights":[],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"http://hdl.handle.net/10464/9502","outbound_label":"Handle","outbound_source":"dc:identifier.uri"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.department","label":"Department","values":["Department of Chemistry"]},{"key":"dc:creator","label":"Author","values":["Richardson, Paul"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.accessioned","label":"Dc Date Accessioned","values":["2016-07-14T19:14:14Z"]},{"key":"dc:date.available","label":"Dc Date Available","values":["2016-07-14T19:14:14Z"]},{"key":"dc:date.issued","label":"Date","values":["2016-07-14T19:14:14Z"]},{"key":"dc:type","label":"Dc Type","values":["Electronic Thesis or Dissertation"]},{"key":"thesis:degree_discipline","label":"Discipline","values":["Faculty of Mathematics and Science"]},{"key":"thesis:degree_level","label":"Degree Level","values":["Masters"]},{"key":"thesis:degree_name","label":"Degree Name","values":["M.Sc. Chemistry"]},{"key":"thesis:institution_name","label":"Thesis Institution Name","values":["Brock University"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["polynuclear 3d/4f-metal clusters","molecular magnetic refrigerants","single-molecule magnets","dioximes","diols"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language.iso","label":"Language (ISO)","values":["eng"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier.uri","label":"Identifier URI","values":["http://hdl.handle.net/10464/9502"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["The use of two different chelating/bridging ligands, naphthalene-2,3-diol (ndH2) and acenaphthenequinone dioxime (acndH2), in heterometallic 3d/4f-metal cluster chemistry has yielded two new families of polynuclear CuII/LnIII clusters. These complexes were found to exhibit interesting magnetic properties, specifically single-molecule magnetism and the magnetocaloric effect. In this thesis, Chapter 1 lays the foundation for the research presented within. This section covers the fundamentals of polynuclear metal complexes, molecular magnetism, and the magnetocaloric effect, as well as the approaches used for the synthesis of new polynuclear metal complexes and the choice of ligands. Chapters 2 and 3 report the results of the current thesis. In Chapter 2, the synthesis and characterization of a family of {Cu4Ln} complexes (LnIII = GdIII (1), TbIII (2), DyIII (3)), employing the ligand ndH2 is presented. The complexes join a handful of previously reported {Cu4Ln} clusters, however, the family reported in this thesis are the first ‘propeller’-like clusters that exhibit single-molecule magnetism and magnetic refrigeration properties. In Chapter 3, a family of {Cu6Ln2}n chains (LnIII = GdIII (4), TbIII (5), DyIII (6)) obtained through the employment of ligand acndH2 is presented. This family of 1D-chains is a novel motif that has not been previously reported in the literature, with only a few discrete {Cu6Ln2} 0D-clusters having been previously reported. The complexes were magnetically characterized, with 4 and 5 exhibiting ferromagnetic exchange interactions while 6 revealed a more complex magnetic behaviour with both ferromagnetic and antiferromagnetic interactions dominating at different temperature regimes. Furthermore, 5 was found to behave as a single-molecule magnet and 4 was shown to act as a molecular magnetic refrigerant."]},{"key":"dc:title","label":"Title","values":["Polynuclear 3d/4f-Metal Complexes as Molecular Magnetic Refrigerants and Single-Molecule Magnets"]}]}],"canonical_facts":{"dc:contributor.department":["Department of Chemistry"],"dc:creator":["Richardson, Paul"],"dc:date.accessioned":["2016-07-14T19:14:14Z"],"dc:date.available":["2016-07-14T19:14:14Z"],"dc:date.issued":["2016-07-14T19:14:14Z"],"dc:description.abstract":["The use of two different chelating/bridging ligands, naphthalene-2,3-diol (ndH2) and acenaphthenequinone dioxime (acndH2), in heterometallic 3d/4f-metal cluster chemistry has yielded two new families of polynuclear CuII/LnIII clusters. These complexes were found to exhibit interesting magnetic properties, specifically single-molecule magnetism and the magnetocaloric effect. In this thesis, Chapter 1 lays the foundation for the research presented within. This section covers the fundamentals of polynuclear metal complexes, molecular magnetism, and the magnetocaloric effect, as well as the approaches used for the synthesis of new polynuclear metal complexes and the choice of ligands. Chapters 2 and 3 report the results of the current thesis. In Chapter 2, the synthesis and characterization of a family of {Cu4Ln} complexes (LnIII = GdIII (1), TbIII (2), DyIII (3)), employing the ligand ndH2 is presented. The complexes join a handful of previously reported {Cu4Ln} clusters, however, the family reported in this thesis are the first ‘propeller’-like clusters that exhibit single-molecule magnetism and magnetic refrigeration properties. In Chapter 3, a family of {Cu6Ln2}n chains (LnIII = GdIII (4), TbIII (5), DyIII (6)) obtained through the employment of ligand acndH2 is presented. This family of 1D-chains is a novel motif that has not been previously reported in the literature, with only a few discrete {Cu6Ln2} 0D-clusters having been previously reported. The complexes were magnetically characterized, with 4 and 5 exhibiting ferromagnetic exchange interactions while 6 revealed a more complex magnetic behaviour with both ferromagnetic and antiferromagnetic interactions dominating at different temperature regimes. Furthermore, 5 was found to behave as a single-molecule magnet and 4 was shown to act as a molecular magnetic refrigerant."],"dc:identifier.uri":["http://hdl.handle.net/10464/9502"],"dc:language.iso":["eng"],"dc:subject":["polynuclear 3d/4f-metal clusters","molecular magnetic refrigerants","single-molecule magnets","dioximes","diols"],"dc:title":["Polynuclear 3d/4f-Metal Complexes as Molecular Magnetic Refrigerants and Single-Molecule Magnets"],"dc:type":["Electronic Thesis or Dissertation"],"thesis:degree_discipline":["Faculty of Mathematics and Science"],"thesis:degree_level":["Masters"],"thesis:degree_name":["M.Sc. Chemistry"],"thesis:institution_name":["Brock University"]},"updated_at":"2026-07-24T01:22:58Z"}