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High pressure studies of hydroxo-bridged Cu(II) dimers
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
Added On:
01/04/2012 13:26
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