{"id":{"repo_id":"uwo","oai_identifier":"oai:uwo.scholaris.ca:20.500.14721/28263"},"canonical_url":"https://search.dev.ndltd.org/etd/uwo/oai:uwo.scholaris.ca:20.500.14721/28263","repository":{"repo_id":"uwo","name":"Western University","base_url":"https://uwo.scholaris.ca/server/oai/request"},"display":{"title":"Coinage Metal Chalcogenide Clusters with N-Heterocyclic Carbene Ancillary Ligands","abstract":"This thesis describes the synthesis and characterization of homo- and heterometallic group 11 – group 16 clusters with N-heterocyclic carbene (NHC) ligands. The clusters were prepared from reactive group 11 trimethylsilylchalcogenolate reagents (NHC-M-ESiMe3; M = Cu, Au; E = S, Se, Te) by silane deprotection reactions with phosphine- or phosphite-solubilized group 11 acetates (R3P-M-OAc; M = Cu, Ag, Au). Clusters were characterized by combustion analysis and spectroscopic methods in solution and the solid state. The clusters were phosphorescent at low temperatures with emission energies that depend on the metal/chalcogen composition, ancillary NHC ligand, cluster geometry and nuclearity, and local environment. Lower energy photoluminescence is associated with higher atomic number chalcogenide ligands and correlates with the M→S metal-to-ligand charge transfer energy, for which M = Ag > Cu > Au. Quantum yield of emission is increased in a cluster of high nuclearity and connectivity because of increased molecular rigidity and thermally activated delayed fluorescence. Quantum chemical calculations point to a common mode of emission from all clusters, originating from a charge transfer process from metal-chalcogenide core to the NHC ancillary ligands.","abstract_html":"This thesis describes the synthesis and characterization of homo- and heterometallic group 11 – group 16 clusters with N-heterocyclic carbene (NHC) ligands. The clusters were prepared from reactive group 11 trimethylsilylchalcogenolate reagents (NHC-M-ESiMe3; M = Cu, Au; E = S, Se, Te) by silane deprotection reactions with phosphine- or phosphite-solubilized group 11 acetates (R3P-M-OAc; M = Cu, Ag, Au). Clusters were characterized by combustion analysis and spectroscopic methods in solution and the solid state. The clusters were phosphorescent at low temperatures with emission energies that depend on the metal/chalcogen composition, ancillary NHC ligand, cluster geometry and nuclearity, and local environment. Lower energy photoluminescence is associated with higher atomic number chalcogenide ligands and correlates with the M→S metal-to-ligand charge transfer energy, for which M = Ag > Cu > Au. Quantum yield of emission is increased in a cluster of high nuclearity and connectivity because of increased molecular rigidity and thermally activated delayed fluorescence. Quantum chemical calculations point to a common mode of emission from all clusters, originating from a charge transfer process from metal-chalcogenide core to the NHC ancillary ligands.","abstract_has_math":false,"creators":["Polgar, Alex"],"institution":"The University of Western Ontario","degree_name":"M Sc","degree_level":null,"degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":[],"advisors":["Corrigan, John F."],"committee_chairs":[],"committee_members":[],"year":2018,"date_issued":"2018-07-18","date_published":"2018-07-18","updated_at":"2026-07-27T21:55:54Z","subjects":["Gold","Silver","Copper","Sulfur","Selenium","Tellurium"],"languages":["en_ca"],"rights":[],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"https://hdl.handle.net/20.500.14721/28263","outbound_label":"Handle","outbound_source":"dc:identifier.uri"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.advisor","label":"Advisor","values":["Corrigan, John F."]},{"key":"dc:creator","label":"Author","values":["Polgar, Alex"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.accessioned","label":"Dc Date Accessioned","values":["2025-07-10T16:09:28Z"]},{"key":"dc:date.available","label":"Dc Date Available","values":["2025-07-10T16:09:28Z"]},{"key":"dc:date.issued","label":"Date","values":["2018-07-18"]},{"key":"dc:publisher","label":"Institution","values":["The University of Western Ontario"]},{"key":"dc:type","label":"Dc Type","values":["thesis"]},{"key":"thesis:degree_discipline","label":"Discipline","values":["Chemistry"]},{"key":"thesis:degree_name","label":"Degree Name","values":["M Sc"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Gold","Silver","Copper","Sulfur","Selenium","Tellurium"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language.iso","label":"Language (ISO)","values":["en_ca"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier.uri","label":"Identifier URI","values":["https://hdl.handle.net/20.500.14721/28263"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["The thesis cover page in the PDF document includes references to Western University’s previous institutional repository platform, known as Scholarship@Western, and links to that platform (beginning with ir.lib.uwo.ca). In citing or referring to this thesis, use the DOI or handle from this page instead. Sample citation: Author name, \"Thesis title.\" (Year). Western University Open Repository. https://doi.org/10.71858/123456."]},{"key":"dc:description.abstract","label":"Abstract","values":["This thesis describes the synthesis and characterization of homo- and heterometallic group 11 – group 16 clusters with N-heterocyclic carbene (NHC) ligands. The clusters were prepared from reactive group 11 trimethylsilylchalcogenolate reagents (NHC-M-ESiMe3; M = Cu, Au; E = S, Se, Te) by silane deprotection reactions with phosphine- or phosphite-solubilized group 11 acetates (R3P-M-OAc; M = Cu, Ag, Au). Clusters were characterized by combustion analysis and spectroscopic methods in solution and the solid state. The clusters were phosphorescent at low temperatures with emission energies that depend on the metal/chalcogen composition, ancillary NHC ligand, cluster geometry and nuclearity, and local environment. Lower energy photoluminescence is associated with higher atomic number chalcogenide ligands and correlates with the M→S metal-to-ligand charge transfer energy, for which M = Ag > Cu > Au. Quantum yield of emission is increased in a cluster of high nuclearity and connectivity because of increased molecular rigidity and thermally activated delayed fluorescence. Quantum chemical calculations point to a common mode of emission from all clusters, originating from a charge transfer process from metal-chalcogenide core to the NHC ancillary ligands."]},{"key":"dc:title","label":"Title","values":["Coinage Metal Chalcogenide Clusters with N-Heterocyclic Carbene Ancillary Ligands"]}]}],"canonical_facts":{"dc:contributor.advisor":["Corrigan, John F."],"dc:creator":["Polgar, Alex"],"dc:date.accessioned":["2025-07-10T16:09:28Z"],"dc:date.available":["2025-07-10T16:09:28Z"],"dc:date.issued":["2018-07-18"],"dc:description":["The thesis cover page in the PDF document includes references to Western University’s previous institutional repository platform, known as Scholarship@Western, and links to that platform (beginning with ir.lib.uwo.ca). In citing or referring to this thesis, use the DOI or handle from this page instead. Sample citation: Author name, \"Thesis title.\" (Year). Western University Open Repository. https://doi.org/10.71858/123456."],"dc:description.abstract":["This thesis describes the synthesis and characterization of homo- and heterometallic group 11 – group 16 clusters with N-heterocyclic carbene (NHC) ligands. The clusters were prepared from reactive group 11 trimethylsilylchalcogenolate reagents (NHC-M-ESiMe3; M = Cu, Au; E = S, Se, Te) by silane deprotection reactions with phosphine- or phosphite-solubilized group 11 acetates (R3P-M-OAc; M = Cu, Ag, Au). Clusters were characterized by combustion analysis and spectroscopic methods in solution and the solid state. The clusters were phosphorescent at low temperatures with emission energies that depend on the metal/chalcogen composition, ancillary NHC ligand, cluster geometry and nuclearity, and local environment. Lower energy photoluminescence is associated with higher atomic number chalcogenide ligands and correlates with the M→S metal-to-ligand charge transfer energy, for which M = Ag > Cu > Au. Quantum yield of emission is increased in a cluster of high nuclearity and connectivity because of increased molecular rigidity and thermally activated delayed fluorescence. Quantum chemical calculations point to a common mode of emission from all clusters, originating from a charge transfer process from metal-chalcogenide core to the NHC ancillary ligands."],"dc:identifier.uri":["https://hdl.handle.net/20.500.14721/28263"],"dc:language.iso":["en_ca"],"dc:publisher":["The University of Western Ontario"],"dc:subject":["Gold","Silver","Copper","Sulfur","Selenium","Tellurium"],"dc:title":["Coinage Metal Chalcogenide Clusters with N-Heterocyclic Carbene Ancillary Ligands"],"dc:type":["thesis"],"thesis:degree_discipline":["Chemistry"],"thesis:degree_name":["M Sc"]},"updated_at":"2026-07-27T21:55:54Z"}