Issue 1, 2010
From the journal:

Dalton Transactions

High pressure studies of hydroxo-bridged Cu(ii) dimers†

Alessandro Prescimone,a   Javier Sanchez-Benitez,b   Konstantin K. Kamenev,b   Stephen A. Moggach,a   John E. Warren,c   Alistair R. Lennie,c   Mark Murrie,d   Simon Parsons*a  and  Euan K. Brechin*a  

* Corresponding authors

a School of Chemistry and Centre for Science at Extreme Conditions, The University of Edinburgh, West Mains Road, Edinburgh, UK
E-mail: ebrechin@staffmail.ed.ac.uk, s.parsons@ed.ac.uk

b School of Engineering and Centre for Science at Extreme Conditions, The University of Edinburgh, West Mains Road, Edinburgh, UK

c Synchrotron Radiation Source, STFC Daresbury Laboratory, Warrington, Cheshire, UK

d Department of Chemistry, University of Glasgow, University Avenue, Glasgow, UK

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. [Cu2(OH)2(H2O)2(tmen)2](ClO4)2 (1; tmen = tetramethylethylenediamine), [Cu2(OH)2(tben)2](ClO4)2 (2; tben = di-tbutylethylenediamine) and [Cu2(OH)2(bpy)2](BF4)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 ∼0.9 GPa for 1, 2 and 3: the exchange becomes less antiferromagnetic in 1 and 2 and more ferromagnetic in 3.

Graphical abstract: High pressure studies of hydroxo-bridged Cu(ii) dimers

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Article information

DOI
https://doi.org/10.1039/B918287J
Article type
Paper
Submitted
04 Sep 2009
Accepted
05 Oct 2009
First published
05 Nov 2009

Dalton Trans., 2010,39, 113-123

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

A. Prescimone, J. Sanchez-Benitez, K. K. Kamenev, S. A. Moggach, J. E. Warren, A. R. Lennie, M. Murrie, S. Parsons and E. K. Brechin, Dalton Trans., 2010, 39, 113 DOI: 10.1039/B918287J

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