Show simple item record

dc.contributor.advisorJones, Dr. Leigh F.
dc.contributor.authorMeally, Seán Tomás
dc.date.accessioned2013-05-08T14:25:52Z
dc.date.available2016-02-11T13:31:32Z
dc.date.issued2012-11-02
dc.identifier.urihttp://hdl.handle.net/10379/3398
dc.description.abstractWe report the synthesis, structural and magnetic characterisation of a family of planar, pseudo metallocalix[6]arene disc-like complexes (1-10 and 14-21) of general formula [M7(OH)6(Lx)6](NO3)2 {M = Ni(II), Zn(II), Co(II/III)} and LxH are Schiff base ligands: L1H = 2-iminomethyl-6-methoxyphenol, L2H = 4-bromo-2-iminomethyl-6-methoxyphenol, L3H = 2-iminophenyl-6-methoxyphenol). Each member exhibits a double-bowl pseudo metallocalix[6]arene topology of which the [M(II)7] units in complexes 1-8 stack on top of one another to generate molecular host cavities in the solid-state, capable of encapsulating a wide variety of guest molecules (MeCN, NO2Me, MeOH). Encapsulation of the reactive aromatic species 2-Furaldehyde and 3-Furaldehyde was also achieved in the form of complexes 14-18; presence of guest furaldehyde species being detected via spectroscopic methods. Dc magnetic susceptibility measurements were performed on complexes 2, 4, 8 and 9 which revealed weak ferromagnetic intramolecular exchange between the Ni(II) ions in both complexes [(MeOH)2¿Ni(II)7(OH)6(L1)6](NO3)2 (2) and [(MeCN)2¿Ni(II)7(OH)6(L2)6](NO3)2 (4), while similar studies on complexes (8-9) revealed weak ferro- and ferrimagnetic behaviour respectively. The ¿¿¿ notation is used to indicate guest presence. Attempts at extending the molecular cavities present in these systems via functionalisation of the utilised Schiff base ligand, led to the isolation of the heptanuclear complexes (19-21) of general formula [M(II)7(OMe)4(OEt)2(L4)6](NO3)2 (where M = Ni(II), Zn(II), Co(II) and L4H = 4-phenyl-2-iminomethyl-6-methoxyphenol). In efforts to expand our family of solid-state host-guest disc-like complexes the Schiff base ligand was further functionalised and other M(II) salt precursors were utilised. These investigations instead afforded entirely different complex topologies including the heterometallic tetranuclear complexes of general formula [Na(I)2M2(X)2(L1)4(Y)2] {where M = Fe(III), X = MeO-, Y = NO3- (24); M = Ni(II), X = N3- and Y = MeCN (25)}, each comprising the molecular butterfly topology. Magnetic susceptibility measurements of these complexes highlight antiferromagnetic and ferromagnetic coupling in 24 and 25 respectively, with the inclusion of the azide bridging anion (N3-) in the latter affording the observed ferromagnetic coupling between the Ni(II) ions. We also report the formation of the heterometallic molecular cage [Na(I)3Ni(II)2(L1)6](ClO4) (28) which exhibits a rare trigonal bipyramidal core topology. In addition we report the isolation of the tetranuclear cubane clusters [Mn(III)3Mn(IV)1(O)3(OEt)(OAc)3(L1)3] (30) and [Ni(II)4(µ3-OMe)4(L5)4(MeOH)4] (32) (where L5H = 2-imino-6-methoxyphenol). Dc and ac magnetic susceptibility studies on complexes 30 and 32 reveal S = 9/2 and S = 4 spin ground states, as a result of ferri- and ferromagnetic exchange coupling in complexes 30 and 32 respectively.en_US
dc.subjectChemistryen_US
dc.subjectHost-Guesten_US
dc.subjectSensorsen_US
dc.subjectGas Storageen_US
dc.subjectDrug Deliveryen_US
dc.subjectInorganicen_US
dc.subjectCoordinationen_US
dc.subjectSupramolecularen_US
dc.subjectEnzymeen_US
dc.subjectNien_US
dc.subjectCoen_US
dc.subjectMeallyen_US
dc.subjectJonesen_US
dc.subjectBrechinen_US
dc.subjectPoweren_US
dc.subjectTransition metalen_US
dc.subjectCubaneen_US
dc.subjectDiscen_US
dc.subjectButterflyen_US
dc.subjectTetranuclearen_US
dc.subjectMononuclearen_US
dc.subjectPolymetallicen_US
dc.subjectPolynuclearen_US
dc.subjectMixed metalen_US
dc.subjectIonen_US
dc.subjectChelationen_US
dc.subjectLigationen_US
dc.subjectBonden_US
dc.subjectAromaticen_US
dc.subjectHydrogen bondingen_US
dc.subjectIntermolecularen_US
dc.titleInvestigating the Structural and Magnetic Characteristics of Polynuclear Complexes including the Solid-State Hosting Abilities of [M7] {M = Ni(II), Zn(II), Co(II/III)} Metallocalix[6]arene Discs.en_US
dc.typeThesisen_US
dc.contributor.funderIrish Research Councilen_US
dc.local.noteThis thesis describes the synthesis of a family of planar metallocalix[6]arene disc complexes. These compounds form molecular cavities in the solid state which allow for encapsulation of a variety of guest molecules. Potential applications of such host-guest systems include gas storage, chemical sensing and medical imaging.en_US
dc.local.finalYesen_US
nui.item.downloads495


Files in this item

Attribution-NonCommercial-NoDerivs 3.0 Ireland
This item is available under the Attribution-NonCommercial-NoDerivs 3.0 Ireland. No item may be reproduced for commercial purposes. Please refer to the publisher's URL where this is made available, or to notes contained in the item itself. Other terms may apply.

The following license files are associated with this item:

Thumbnail
Thumbnail

This item appears in the following Collection(s)

Show simple item record