{"id":{"repo_id":"auckland-ms","oai_identifier":"oai:researchspace.auckland.ac.nz:2292/62574"},"canonical_url":"https://search.dev.ndltd.org/etd/auckland-ms/oai:researchspace.auckland.ac.nz:2292/62574","repository":{"repo_id":"auckland-ms","name":"University of Auckland","base_url":"https://researchspace.auckland.ac.nz/server/oai/request"},"display":{"title":"Ferrocene-derived Heterobimetallic Supramolecular Architectures: Synthesis, Guest Encapsulation and Stimulus-Responsive Studies","abstract":"Metallosupramolecular architectures are increasing in popularity due to their range of applications and ease of self-assembly. Many are able to readily change their shape and/or function in response to external stimuli and have the ability to encapsulate guest molecules within their internal cavities. As the majority of studies into homometallic stimuli-responsive supramolecular systems has focused on total disassembly of the architecture, this provided an opportunity to explore reversible partial disassembly and reassembly by which the entire host structure remains intact. As such, this project was centred on fashioning reversible stimulus-initiated heterobimetallic supramolecular structures whereby the structures would undergo partial disassembly when an external stimulus is applied and reassemble when the stimulus is removed. Heterobimetallic [PdmLn]x+ complexes bearing symmetrical ferrocene-derived ligands through the formation of Pd–pyridyl bonds have been designed to allow for disassembly and reassembly. The formation of a series of PdL, PdL2 or Pd2L4 structures was possible through controlling the substitution pattern of the coordinating pyridyl rings. Cleavage of the relatively labile Pd–Npyridyl donor bonds, and subsequent disassembly of the supramolecular structure, was achieved through competitive ligand binding with N,N’-dimethylaminopyridine or a Cl- source to form PdCl42-. Triggering complex reassembly was successful for several complexes upon the addition of H+ or Ag+. Guest binding studies revealed interactions with several compounds with the anionic guests p-toluenesulfonate and octyl sulfate, and their binding constants were calculated based on 1H NMR spectroscopy experiments. Alternatively, dis- and reassembling structures can be obtained by introducing heteroditopic ligand systems. A ruthenium(II) heterobimetallic supramolecular structure bearing a non-symmetrically functionalised ferrocenyl ligand was designed to respond to the exposure and removal of light. Ru(II) complexes are well known for their ability to undergo photo-induced ligand ejection, in particular Ru–N bonds. The Ru(II) moiety was attached through a stable Ru–NHC (N-heterocyclic carbene) coordination bond on one arm of the ferrocenyl ligand and a more labile coordination to a pyridyl-triazole group on the other. While the final complex proved challenging to purify for light-responsiveness and guest binding studies, the synthetic routes towards the formation of the target ferrocenyl ligands and Ru(II) complexes are described in detail.","abstract_html":"Metallosupramolecular architectures are increasing in popularity due to their range of applications and ease of self-assembly. Many are able to readily change their shape and/or function in response to external stimuli and have the ability to encapsulate guest molecules within their internal cavities. As the majority of studies into homometallic stimuli-responsive supramolecular systems has focused on total disassembly of the architecture, this provided an opportunity to explore reversible partial disassembly and reassembly by which the entire host structure remains intact. As such, this project was centred on fashioning reversible stimulus-initiated heterobimetallic supramolecular structures whereby the structures would undergo partial disassembly when an external stimulus is applied and reassemble when the stimulus is removed. Heterobimetallic [PdmLn]x+ complexes bearing symmetrical ferrocene-derived ligands through the formation of Pd–pyridyl bonds have been designed to allow for disassembly and reassembly. The formation of a series of PdL, PdL2 or Pd2L4 structures was possible through controlling the substitution pattern of the coordinating pyridyl rings. Cleavage of the relatively labile Pd–Npyridyl donor bonds, and subsequent disassembly of the supramolecular structure, was achieved through competitive ligand binding with N,N’-dimethylaminopyridine or a Cl- source to form PdCl42-. Triggering complex reassembly was successful for several complexes upon the addition of H+ or Ag+. Guest binding studies revealed interactions with several compounds with the anionic guests p-toluenesulfonate and octyl sulfate, and their binding constants were calculated based on 1H NMR spectroscopy experiments. Alternatively, dis- and reassembling structures can be obtained by introducing heteroditopic ligand systems. A ruthenium(II) heterobimetallic supramolecular structure bearing a non-symmetrically functionalised ferrocenyl ligand was designed to respond to the exposure and removal of light. Ru(II) complexes are well known for their ability to undergo photo-induced ligand ejection, in particular Ru–N bonds. The Ru(II) moiety was attached through a stable Ru–NHC (N-heterocyclic carbene) coordination bond on one arm of the ferrocenyl ligand and a more labile coordination to a pyridyl-triazole group on the other. While the final complex proved challenging to purify for light-responsiveness and guest binding studies, the synthetic routes towards the formation of the target ferrocenyl ligands and Ru(II) complexes are described in detail.","abstract_has_math":false,"creators":["Tremlett, William D. J."],"institution":"ResearchSpace@Auckland","degree_name":"PhD","degree_level":"Doctoral","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":[],"advisors":["Hartinger, Christian"],"committee_chairs":[],"committee_members":[],"year":2022,"date_issued":"2022","date_published":"2022","updated_at":"2026-07-24T01:07:07Z","subjects":[],"languages":[],"rights":["Items in ResearchSpace are protected by copyright, with all rights reserved, unless otherwise indicated."],"rights_urls":["https://researchspace.auckland.ac.nz/docs/uoa-docs/rights.htm"],"identifier_entries":[]},"links":{"outbound_url":"https://hdl.handle.net/2292/62574","outbound_label":"Handle","outbound_source":"dc:identifier.uri"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.advisor","label":"Advisor","values":["Hartinger, Christian"]},{"key":"dc:creator","label":"Author","values":["Tremlett, William D. 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Many are able to readily change their shape and/or function in response to external stimuli and have the ability to encapsulate guest molecules within their internal cavities. As the majority of studies into homometallic stimuli-responsive supramolecular systems has focused on total disassembly of the architecture, this provided an opportunity to explore reversible partial disassembly and reassembly by which the entire host structure remains intact. As such, this project was centred on fashioning reversible stimulus-initiated heterobimetallic supramolecular structures whereby the structures would undergo partial disassembly when an external stimulus is applied and reassemble when the stimulus is removed. Heterobimetallic [PdmLn]x+ complexes bearing symmetrical ferrocene-derived ligands through the formation of Pd–pyridyl bonds have been designed to allow for disassembly and reassembly. The formation of a series of PdL, PdL2 or Pd2L4 structures was possible through controlling the substitution pattern of the coordinating pyridyl rings. Cleavage of the relatively labile Pd–Npyridyl donor bonds, and subsequent disassembly of the supramolecular structure, was achieved through competitive ligand binding with N,N’-dimethylaminopyridine or a Cl- source to form PdCl42-. Triggering complex reassembly was successful for several complexes upon the addition of H+ or Ag+. Guest binding studies revealed interactions with several compounds with the anionic guests p-toluenesulfonate and octyl sulfate, and their binding constants were calculated based on 1H NMR spectroscopy experiments. Alternatively, dis- and reassembling structures can be obtained by introducing heteroditopic ligand systems. A ruthenium(II) heterobimetallic supramolecular structure bearing a non-symmetrically functionalised ferrocenyl ligand was designed to respond to the exposure and removal of light. Ru(II) complexes are well known for their ability to undergo photo-induced ligand ejection, in particular Ru–N bonds. The Ru(II) moiety was attached through a stable Ru–NHC (N-heterocyclic carbene) coordination bond on one arm of the ferrocenyl ligand and a more labile coordination to a pyridyl-triazole group on the other. While the final complex proved challenging to purify for light-responsiveness and guest binding studies, the synthetic routes towards the formation of the target ferrocenyl ligands and Ru(II) complexes are described in detail."]},{"key":"dc:title","label":"Title","values":["Ferrocene-derived Heterobimetallic Supramolecular Architectures: Synthesis, Guest Encapsulation and Stimulus-Responsive Studies"]}]}],"canonical_facts":{"dc:contributor.advisor":["Hartinger, Christian"],"dc:creator":["Tremlett, William D. J."],"dc:date.accessioned":["2023-01-25T01:42:29Z"],"dc:date.available":["2023-01-25T01:42:29Z"],"dc:date.issued":["2022"],"dc:description.abstract":["Metallosupramolecular architectures are increasing in popularity due to their range of applications and ease of self-assembly. Many are able to readily change their shape and/or function in response to external stimuli and have the ability to encapsulate guest molecules within their internal cavities. As the majority of studies into homometallic stimuli-responsive supramolecular systems has focused on total disassembly of the architecture, this provided an opportunity to explore reversible partial disassembly and reassembly by which the entire host structure remains intact. As such, this project was centred on fashioning reversible stimulus-initiated heterobimetallic supramolecular structures whereby the structures would undergo partial disassembly when an external stimulus is applied and reassemble when the stimulus is removed. Heterobimetallic [PdmLn]x+ complexes bearing symmetrical ferrocene-derived ligands through the formation of Pd–pyridyl bonds have been designed to allow for disassembly and reassembly. The formation of a series of PdL, PdL2 or Pd2L4 structures was possible through controlling the substitution pattern of the coordinating pyridyl rings. Cleavage of the relatively labile Pd–Npyridyl donor bonds, and subsequent disassembly of the supramolecular structure, was achieved through competitive ligand binding with N,N’-dimethylaminopyridine or a Cl- source to form PdCl42-. Triggering complex reassembly was successful for several complexes upon the addition of H+ or Ag+. Guest binding studies revealed interactions with several compounds with the anionic guests p-toluenesulfonate and octyl sulfate, and their binding constants were calculated based on 1H NMR spectroscopy experiments. Alternatively, dis- and reassembling structures can be obtained by introducing heteroditopic ligand systems. A ruthenium(II) heterobimetallic supramolecular structure bearing a non-symmetrically functionalised ferrocenyl ligand was designed to respond to the exposure and removal of light. Ru(II) complexes are well known for their ability to undergo photo-induced ligand ejection, in particular Ru–N bonds. The Ru(II) moiety was attached through a stable Ru–NHC (N-heterocyclic carbene) coordination bond on one arm of the ferrocenyl ligand and a more labile coordination to a pyridyl-triazole group on the other. While the final complex proved challenging to purify for light-responsiveness and guest binding studies, the synthetic routes towards the formation of the target ferrocenyl ligands and Ru(II) complexes are described in detail."],"dc:identifier.uri":["https://hdl.handle.net/2292/62574"],"dc:publisher":["ResearchSpace@Auckland"],"dc:relation.isreferencedby":["UoA"],"dc:rights":["Items in ResearchSpace are protected by copyright, with all rights reserved, unless otherwise indicated."],"dc:rights.uri":["https://researchspace.auckland.ac.nz/docs/uoa-docs/rights.htm"],"dc:title":["Ferrocene-derived Heterobimetallic Supramolecular Architectures: Synthesis, Guest Encapsulation and Stimulus-Responsive Studies"],"dc:type":["Thesis"],"thesis:degree_discipline":["Chemistry"],"thesis:degree_level":["Doctoral"],"thesis:degree_name":["PhD"],"thesis:institution_name":["The University of Auckland"]},"updated_at":"2026-07-24T01:07:07Z"}