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Details of Grant 

EPSRC Reference: GR/R46021/01
Title: New Ligands for High Spin Cages ans Single Molecule Magnets
Principal Investigator: Winpenny, Professor RE
Other Investigators:
Researcher Co-Investigators:
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Department: Chemistry
Organisation: University of Manchester, The
Scheme: Standard Research (Pre-FEC)
Starts: 29 October 2001 Ends: 28 October 2004 Value (£): 219,218
EPSRC Research Topic Classifications:
Co-ordination Chemistry
EPSRC Industrial Sector Classifications:
No relevance to Underpinning Sectors Electronics
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Panel History:  
Summary on Grant Application Form
Synthesis of paramagnetic polymetallic complexes is largely dependent on the ligands used. Previous work has relied on a very limited range of ligands, here we propose to examine two classes of ligand which have not been used previously. The first are phosphonates/arsonates, which have been widely used in generating 2D materials but rarely for molecular clusters. Preliminary results demonstrate that two routes will be fruitful. The first involves reacting phosphonates/arsonates with metal salts in the presence of a co-ligand, with the phosphonate at low mole ratios to prevent formation of insoluble materials. This has produced a tidecanuclear Co cage. Secondly, the ligands can displace carboxylates from pre-formed cages, with the presence of the additional oxygen atom within the phosphonate leading to linking of the clusters. This has already generated a hexadecanuclear Mn cage. This second strategy can be developed by reaction of a range of small cages with phosphonate/arsonate ligands. The second ligands are pyrazalinones, which have already been shown to generate a Ni24 cage. Two routes to new cages using these ligands are also outlined. These routes are: reaction of the pyrazalinones, with metal carboxylates, and reaction of a mononuclear complex of the ligands with metal salts. This latter reaction shows considerable promise for generating heterometallic cages. The cages will be characterized by X-ray crystallography, and their magnetic properties studied by susceptability measurements, EPR spectroscopy and inelastic neutrun scattering.
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Organisation Website: http://www.man.ac.uk