Supramolecular Synthesis of Molecular Clusters: Topological Control of Hybrid Nanomagnets

Lead Research Organisation: Heriot-Watt University
Department Name: Sch of Engineering and Physical Science

Abstract

Polynuclear cages of paramagnetic transition metal ions can exhibit fascinating physical properties and have great potential in the field of single molecule magnetism and molecular spintronics. Supramolecular chemistry is defined as chemistry beyond the molecule, and examines (amongst other things) intermolecular interactions. Such interactions (e.g. hydrogen bonding) can have profound effects on the bulk phase of molecular nanomagnets (MNM) and we propose to modulate the interactions found between MNMs by marrying the two areas of research. We are going to approach this problem in two different yet intimately related ways with cyclic cavity containing molecules called calixarenes. These molecules can be functionalised with relative ease, and can also be combined with other small molecules to make covalent cage structures. In order to modulate these interactions we will a) form metal clusters within these cages, b) substitute groups on MNMs with functional calixarenes, and c) make 3-D arrays of MNMs with single calixarenes or molecular cages. Dr. Scott J. Dalgarno has expertise in calixarene synthesis and crystallographic studies on large supramolecular systems and Dr. Euan K. Brechin is a world leader in molecular magnetism. These techniques will be critical in elucidating the modulation of the intermolecular interactions, and will allow us to tune the magnetic properties of the resulting metal clusters for potential exploitation in the aforementioned fields of application.

Publications

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Fairbairn RE (2012) Calixarene-supported rare-earth clusters: heteroatom bridge influences cluster composition. in Chemical communications (Cambridge, England)

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Karotsis G (2010) [Mn(III)4Ln(III)4] calix[4]arene clusters as enhanced magnetic coolers and molecular magnets. in Journal of the American Chemical Society

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Karotsis G (2010) Calixarene supported enneanuclear Cu(II) clusters. in Chemical communications (Cambridge, England)

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Sanz S (2011) Calix[4]arene-supported Fe(III)2Ln(III)2 clusters. in Chemical communications (Cambridge, England)

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Sanz S (2012) Calix[4]arene-supported rare earth octahedra in Chem. Commun.

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Taylor SM (2011) Calix[4]arene supported clusters: a dimer of [Mn(III)Mn(II)] dimers. in Chemical communications (Cambridge, England)

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Taylor SM (2012) Oxacalix[3]arene-supported supertetrahedron. in Chemical communications (Cambridge, England)

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Taylor SM (2012) p-tert-Butylcalix[8]arene: an extremely versatile platform for cluster formation. in Chemistry (Weinheim an der Bergstrasse, Germany)

 
Description We have discovered and reported a range of new polynuclear metal clusters that have fascinating magnetic properties (Single Molecule Magnets and Magnetic Refrigerants. In doing so we have learned much about the coordination chemistry of some ligands commonly used in supramolecular chemistry.
Exploitation Route This work has afforded a series of metal ion binding rules for the host molecules we studied. These are being put to use in the smart design of cluster materials.
Sectors Chemicals,Energy

URL http://www.che.hw.ac.uk/sjd/Research.htm
 
Description Our findings have been used in further research under EP/I03255X, as well as by other research groups that have investigated related areas of supramolecular coordination chemistry.
First Year Of Impact 2011
Sector Chemicals,Education,Other
Impact Types Societal,Economic