Galloway, Kyle W.
New routes to single molecule magnets.
PhD thesis, University of Glasgow.
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Structural and magnetic studies of citrate coordination clusters are presented for reaction systems involving cobalt(II), copper(II) and nickel(II). The cobalt(II) compounds incorporate cubane structural motifs that are of particular interest for the generation of single molecule magnet (SMM) behaviour. The product family includes a Co4 SMM cluster, a Co6 SMM cluster and a 3D network of linked SMM units. A new route to the erinaceous Co6 cluster crystals is reported, which allows further investigation of the hydration dependent magnetic behaviour of the samples. The structures of a range of copper(II) cluster sizes are described, including a monomer, dimers, trimers and a tetramer. Correlations between structure and magnetic properties are discussed, including the important structural role of the citrate ligand. Two types of citrate-based copper(II) dimers are shown to undergo unusual structural transformations at high pressure. Initial results of the development of 3d-4f systems based on cobalt(II) and copper(II) are described, including a discussion of reaction methodology. Finally, a brief examination of the nickel(II) citrate system includes an overview of the complicated synthetic conditions, then considers the magnetic properties of the nickel(II) analogue of the Co4 cluster.
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