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High pressure studies of hydroxo-bridged Cu(II) dimers

DOI: 10.1039/b918287j DOI Help

Authors: Alessandro Prescimone (School of Chemistry and Centre for Science at Extreme Conditions, The University of Edinburgh, U.K.) , Javier Sanchez-benitez (School of Engineering and Centre for Science at Extreme Conditions, The University of Edinburgh, U.K.) , Konstantin K. Kamenev (School of Engineering and Centre for Science at Extreme Conditions, The University of Edinburgh, U.K.) , Stephen Moggach (The University of Edinburgh) , John Warren (University of Liverpool) , Alistair Lennie (Diamond Light Source) , Mark Murrie (Department of Chemistry, University of Glasgow, U.K.) , Simon Parsons (School of Chemistry and Centre for Science at Extreme Conditions, The University of Edinburgh, U.K.) , Euan K. Brechin (School of Chemistry and Centre for Science at Extreme Conditions, The University of Edinburgh, U.K.)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Dalton Transactions , VOL 39

State: Published (Approved)
Published: January 2010

Abstract: A combination of high pressure single crystal X-ray diffraction and high pressure SQUID magnetometry has been used to study three hydroxo-bridged copper(II) dimers. [Cu(2)(OH)(2)(H(2)O)(2)(tmen)(2)](ClO(4))(2) (1; tmen = tetramethylethylenediamine), [Cu(2)(OH)(2)(tben)(2)](ClO(4))(2) (2; tben = di-(t)butylethylenediamine) and [Cu(2)(OH)(2)(bpy)(2)](BF(4))(2) (3; bpy = 2,2'-bipyridine) have been structurally determined to 2.5, 0.9 and 4.7 GPa, respectively. The application of hydrostatic pressure imposes significant distortions and modifications in the structures of all three complexes. This is particularly true of the bond distances and angles between the metal centres and the bridging hydroxo groups. Compound 1 undergoes a phase transition between 1.2 and 2.5 GPa caused by the loss of a coordinated water molecule. This leads to a loss of symmetry and dramatic changes in the molecular structure of the complex. The structural changes are manifested in changes in the magnetic behaviour of the complexes as seen in dc susceptibility measurements up to similar to 0.9 GPa for 1, 2 and 3: the exchange becomes less antiferromagnetic in 1 and 2 and more ferromagnetic in 3.

Journal Keywords: High Pressure Single Crystal X-Ray Diffraction; High Pressure Squid Magnetometry; Hydroxo-Bridged Copper(Ii) Dimers.

Subject Areas: Chemistry

Facility: Daresbury

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