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Synthesis and Characterisation of Lanthanide Complexes as Possible Single-Molecule Magnets
[Thesis]. Manchester, UK: The University of Manchester; 2016.
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Abstract
A range of lanthanide compounds incorporating soft bridging ligands or alkoxide ligands have been synthesised and their magnetic properties investigated. These two classes of compound have shown promise as single molecule magnets but have not been widely studied; this thesis aims to expand on this area of research. Softer bridging ligands are found to slightly increase superexchange interactions between metal centres compared to harder bridging ligands.The introduction to this thesis covers the basic properties of the lanthanides, paying special attention to their chemistry with soft donor ligands and alkoxide ligands. Also included is an introduction to the field of single-molecule magnetism and the role of lanthanide complexes in the study of this behaviour.In Chapter 2, four complexes are reported: the phosphine adducts [Cp’3Ln(H2PMes)] and the phosphide-bridged trimers [(Cp’2)Ln(μ-PHMes)]3 (Ln = Er, Gd). Their structures and magnetic properties are characterised.In Chapter 3, the novel dodecametallic thiolate-bridged lanthanide macrocycles [(Cp’2Ln)3({μ-SCH2}3CMe)]4 (Ln = Dy, Y, Gd) are reported and characterised by X-ray crystallography, NMR spectroscopy and magnetometry. [(Cp’2Dy)3({μ-SCH2}3CMe)]4 is shown to be a single-molecule magnet with Ueff = 69 cm-1.In Chapter 4, the novel thiolate-bridged lanthanide dimers [Cp’2Ln(μ-SCH2{C4H7S2})]2 (Ln = Dy, Y, Gd) are reported, showing sulfur-sulfur bonding leading to ring cyclisation of the bridging ligand [MeC(CH2S)3]3-. These complexes are characterised by X-ray crystallography, NMR spectroscopy and magnetometry. Extra NMR spectroscopic studies were performed to investigate the mechanism of ring closure on the bridging ligand. [Cp’2Dy(μ-SCH2{C4H7S2})]2 is shown to be a single-molecule magnet with Ueff = 87 cm-1.In Chapter 5, four new lanthanide siloxide clusters incorporating alkali metals are reported: the trigonal bipyramidal [Dy2K3(OSiMe3)9]; the octahedral [Dy2K4(OSiMe3)10]; the bi-capped cuboid [Y4K6O6(OSiMe3)12]6-; and the [Dy3K8O3(OSiMe3)12]- ‘burger’ cluster. All clusters are structurally characterised by X-ray crystallography and [Dy2K4(OSiMe3)10] is magnetically characterised. The synthetic rationalisation for formation of these diverse structures is investigated.