{"id":{"repo_id":"birmingham","oai_identifier":"oai:etheses.bham.ac.uk:95"},"canonical_url":"https://search.dev.ndltd.org/etd/birmingham/oai:etheses.bham.ac.uk:95","repository":{"repo_id":"birmingham","name":"University of Birmingham","base_url":"https://etheses.bham.ac.uk/cgi/oai2"},"display":{"title":"Coordination chemistry of cis,trans-1,3,5-Triaminocyclohexane : from mononuclear complexes to supramolecular architectures","abstract":"The coordination chemistry of the rigid, aliphatic triamino ligand \\(cis,trans\\)-1,3,5-triaminocyclohexane (\\(trans\\)-tach) is investigated. With closed shell transition metals, \\(trans\\)-tach forms 1-D {Ag(OTf), ZnCl\\(_2\\)} networks and a 3-D {AgNO\\(_3\\)} coordination polymer with unprecedented topology. Coordination to the open shell transition metals {NiCl\\(_2\\), Ni(NO\\(_3\\))\\(_2\\), Cu(NO\\(_3\\))\\(_2\\), CuBr\\(_2\\), CuCl\\(_2\\), CuF\\(_2\\), CuSO\\(_4\\)} leads to discrete diligand complexes. Protonation of the copper(II) complexes predominantly forms monoligand species, which can aggregate into higher nuclearity clusters. Protonated Cu(NO\\(_3\\))\\(_2\\) and CuBr\\(_2\\) complexes (HNO\\(_3\\) and HBr, respectively) remain mononuclear. CuCl\\(_2\\) and CuBr\\(_2\\) complexes protonated with HCl, however, form trinuclear species comprising trigonal planar \\(\\mu_3\\)-chloro ligands that aggregate into 1-D trinuclear copper(II) chains via hydrogen-bonded interactions. Protonated CuF\\(_2\\) forms a tetranuclear cubane type structure that aggregates into a 3-D nanoporous network via hydrogen-bonded interactions. Protonation of the CuSO\\(_4\\) diligand complex maintains the diligand coordination, forming a 1-D nanoporous network through hydrogen-bonded interactions. Coordination to square planar palladium(II) ions forms all possible coordination motifs (‘Tail’ = monodentate, ‘Head’ = bidentate coordination). ‘Head-to-Head’ coordination results in diligand complexes, ‘Head-to-Tail’ coordination forms cyclic hexanuclear structures and ‘Tail-to-Tail’ coordination leads to a trinuclear species. Extension of \\(trans\\)-tach via Schiff base formation with pyridine-2-carboxaldehyde results in a hexadonor ligand suitable for metal coordination. Depending on the stoichiometry of the metal, mono- or polynuclear complexes are formed.","abstract_html":"The coordination chemistry of the rigid, aliphatic triamino ligand \\(cis,trans\\)-1,3,5-triaminocyclohexane (\\(trans\\)-tach) is investigated. With closed shell transition metals, \\(trans\\)-tach forms 1-D {Ag(OTf), ZnCl<span class=\"etd-inline-math\"><sub>2</sub></span>} networks and a 3-D {AgNO<span class=\"etd-inline-math\"><sub>3</sub></span>} coordination polymer with unprecedented topology. Coordination to the open shell transition metals {NiCl<span class=\"etd-inline-math\"><sub>2</sub></span>, Ni(NO<span class=\"etd-inline-math\"><sub>3</sub></span>)<span class=\"etd-inline-math\"><sub>2</sub></span>, Cu(NO<span class=\"etd-inline-math\"><sub>3</sub></span>)<span class=\"etd-inline-math\"><sub>2</sub></span>, CuBr<span class=\"etd-inline-math\"><sub>2</sub></span>, CuCl<span class=\"etd-inline-math\"><sub>2</sub></span>, CuF<span class=\"etd-inline-math\"><sub>2</sub></span>, CuSO<span class=\"etd-inline-math\"><sub>4</sub></span>} leads to discrete diligand complexes. Protonation of the copper(II) complexes predominantly forms monoligand species, which can aggregate into higher nuclearity clusters. Protonated Cu(NO<span class=\"etd-inline-math\"><sub>3</sub></span>)<span class=\"etd-inline-math\"><sub>2</sub></span> and CuBr<span class=\"etd-inline-math\"><sub>2</sub></span> complexes (HNO<span class=\"etd-inline-math\"><sub>3</sub></span> and HBr, respectively) remain mononuclear. CuCl<span class=\"etd-inline-math\"><sub>2</sub></span> and CuBr<span class=\"etd-inline-math\"><sub>2</sub></span> complexes protonated with HCl, however, form trinuclear species comprising trigonal planar <span class=\"etd-inline-math\">&mu;<sub>3</sub></span>-chloro ligands that aggregate into 1-D trinuclear copper(II) chains via hydrogen-bonded interactions. Protonated CuF<span class=\"etd-inline-math\"><sub>2</sub></span> forms a tetranuclear cubane type structure that aggregates into a 3-D nanoporous network via hydrogen-bonded interactions. Protonation of the CuSO<span class=\"etd-inline-math\"><sub>4</sub></span> diligand complex maintains the diligand coordination, forming a 1-D nanoporous network through hydrogen-bonded interactions. Coordination to square planar palladium(II) ions forms all possible coordination motifs (‘Tail’ = monodentate, ‘Head’ = bidentate coordination). ‘Head-to-Head’ coordination results in diligand complexes, ‘Head-to-Tail’ coordination forms cyclic hexanuclear structures and ‘Tail-to-Tail’ coordination leads to a trinuclear species. Extension of \\(trans\\)-tach via Schiff base formation with pyridine-2-carboxaldehyde results in a hexadonor ligand suitable for metal coordination. Depending on the stoichiometry of the metal, mono- or polynuclear complexes are formed.","abstract_has_math":true,"creators":["Seeber, Georg Peter Maria"],"institution":"University of Birmingham","degree_name":"d_ph","degree_level":"d_ph","degree_discipline":null,"degree_department":null,"school":null,"contributors":[],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2003,"date_issued":"2003-12","date_published":"2003-12","updated_at":"2026-07-24T01:10:41Z","subjects":["QD Chemistry"],"languages":[],"rights":[],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"http://etheses.bham.ac.uk//id/eprint/95/4/Decl_IS_Seeber03PhD.jpg","outbound_label":"Repository record","outbound_source":"dc:identifier.uri"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.sponsor","label":"Sponsor","values":["na"]},{"key":"dc:creator","label":"Author","values":["Seeber, Georg Peter Maria"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2003-12"]},{"key":"dc:date.issued","label":"Date","values":["2003-12"]},{"key":"dc:publisher.department","label":"Dc Publisher Department","values":["School of Chemical Sciences","School of Chemistry"]},{"key":"dc:publisher.institution","label":"Dc Publisher Institution","values":["University of Birmingham"]},{"key":"dc:relation.isreferencedby","label":"Dc Relation Isreferencedby","values":["http://etheses.bham.ac.uk//id/eprint/95/"]},{"key":"dc:type","label":"Dc Type","values":["Thesis"]},{"key":"dc:type.qualificationlevel","label":"Dc Type Qualificationlevel","values":["d_ph"]},{"key":"dc:type.qualificationname","label":"Dc Type Qualificationname","values":["d_ph"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["QD Chemistry"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier.uri","label":"Identifier URI","values":["http://etheses.bham.ac.uk//id/eprint/95/1/Seeber03PhD01.pdf","http://etheses.bham.ac.uk//id/eprint/95/2/Seeber03PhD02.pdf","http://etheses.bham.ac.uk//id/eprint/95/3/Seeber03PhD03.pdf","http://etheses.bham.ac.uk//id/eprint/95/4/Decl_IS_Seeber03PhD.jpg"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["The coordination chemistry of the rigid, aliphatic triamino ligand \\(cis,trans\\)-1,3,5-triaminocyclohexane (\\(trans\\)-tach) is investigated. With closed shell transition metals, \\(trans\\)-tach forms 1-D {Ag(OTf), ZnCl\\(_2\\)} networks and a 3-D {AgNO\\(_3\\)} coordination polymer with unprecedented topology. Coordination to the open shell transition metals {NiCl\\(_2\\), Ni(NO\\(_3\\))\\(_2\\), Cu(NO\\(_3\\))\\(_2\\), CuBr\\(_2\\), CuCl\\(_2\\), CuF\\(_2\\), CuSO\\(_4\\)} leads to discrete diligand complexes. Protonation of the copper(II) complexes predominantly forms monoligand species, which can aggregate into higher nuclearity clusters. Protonated Cu(NO\\(_3\\))\\(_2\\) and CuBr\\(_2\\) complexes (HNO\\(_3\\) and HBr, respectively) remain mononuclear. CuCl\\(_2\\) and CuBr\\(_2\\) complexes protonated with HCl, however, form trinuclear species comprising trigonal planar \\(\\mu_3\\)-chloro ligands that aggregate into 1-D trinuclear copper(II) chains via hydrogen-bonded interactions. Protonated CuF\\(_2\\) forms a tetranuclear cubane type structure that aggregates into a 3-D nanoporous network via hydrogen-bonded interactions. Protonation of the CuSO\\(_4\\) diligand complex maintains the diligand coordination, forming a 1-D nanoporous network through hydrogen-bonded interactions. Coordination to square planar palladium(II) ions forms all possible coordination motifs (‘Tail’ = monodentate, ‘Head’ = bidentate coordination). ‘Head-to-Head’ coordination results in diligand complexes, ‘Head-to-Tail’ coordination forms cyclic hexanuclear structures and ‘Tail-to-Tail’ coordination leads to a trinuclear species. Extension of \\(trans\\)-tach via Schiff base formation with pyridine-2-carboxaldehyde results in a hexadonor ligand suitable for metal coordination. Depending on the stoichiometry of the metal, mono- or polynuclear complexes are formed."]},{"key":"dc:format","label":"Dc Format","values":["application/pdf","image/jpeg"]},{"key":"dc:title","label":"Title","values":["Coordination chemistry of cis,trans-1,3,5-Triaminocyclohexane : from mononuclear complexes to supramolecular architectures"]}]}],"canonical_facts":{"dc:contributor.sponsor":["na"],"dc:creator":["Seeber, Georg Peter Maria"],"dc:date":["2003-12"],"dc:date.issued":["2003-12"],"dc:description.abstract":["The coordination chemistry of the rigid, aliphatic triamino ligand \\(cis,trans\\)-1,3,5-triaminocyclohexane (\\(trans\\)-tach) is investigated. With closed shell transition metals, \\(trans\\)-tach forms 1-D {Ag(OTf), ZnCl\\(_2\\)} networks and a 3-D {AgNO\\(_3\\)} coordination polymer with unprecedented topology. Coordination to the open shell transition metals {NiCl\\(_2\\), Ni(NO\\(_3\\))\\(_2\\), Cu(NO\\(_3\\))\\(_2\\), CuBr\\(_2\\), CuCl\\(_2\\), CuF\\(_2\\), CuSO\\(_4\\)} leads to discrete diligand complexes. Protonation of the copper(II) complexes predominantly forms monoligand species, which can aggregate into higher nuclearity clusters. Protonated Cu(NO\\(_3\\))\\(_2\\) and CuBr\\(_2\\) complexes (HNO\\(_3\\) and HBr, respectively) remain mononuclear. CuCl\\(_2\\) and CuBr\\(_2\\) complexes protonated with HCl, however, form trinuclear species comprising trigonal planar \\(\\mu_3\\)-chloro ligands that aggregate into 1-D trinuclear copper(II) chains via hydrogen-bonded interactions. Protonated CuF\\(_2\\) forms a tetranuclear cubane type structure that aggregates into a 3-D nanoporous network via hydrogen-bonded interactions. Protonation of the CuSO\\(_4\\) diligand complex maintains the diligand coordination, forming a 1-D nanoporous network through hydrogen-bonded interactions. Coordination to square planar palladium(II) ions forms all possible coordination motifs (‘Tail’ = monodentate, ‘Head’ = bidentate coordination). ‘Head-to-Head’ coordination results in diligand complexes, ‘Head-to-Tail’ coordination forms cyclic hexanuclear structures and ‘Tail-to-Tail’ coordination leads to a trinuclear species. Extension of \\(trans\\)-tach via Schiff base formation with pyridine-2-carboxaldehyde results in a hexadonor ligand suitable for metal coordination. Depending on the stoichiometry of the metal, mono- or polynuclear complexes are formed."],"dc:format":["application/pdf","image/jpeg"],"dc:identifier.uri":["http://etheses.bham.ac.uk//id/eprint/95/1/Seeber03PhD01.pdf","http://etheses.bham.ac.uk//id/eprint/95/2/Seeber03PhD02.pdf","http://etheses.bham.ac.uk//id/eprint/95/3/Seeber03PhD03.pdf","http://etheses.bham.ac.uk//id/eprint/95/4/Decl_IS_Seeber03PhD.jpg"],"dc:publisher.department":["School of Chemical Sciences","School of Chemistry"],"dc:publisher.institution":["University of Birmingham"],"dc:relation.isreferencedby":["http://etheses.bham.ac.uk//id/eprint/95/"],"dc:subject":["QD Chemistry"],"dc:title":["Coordination chemistry of cis,trans-1,3,5-Triaminocyclohexane : from mononuclear complexes to supramolecular architectures"],"dc:type":["Thesis"],"dc:type.qualificationlevel":["d_ph"],"dc:type.qualificationname":["d_ph"]},"updated_at":"2026-07-24T01:10:41Z"}