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

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

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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)(H2O)(2)(tmen)(2)](ClO4)(2) (1; tmen = tetramethylethylenediamine), [Cu-2(OH)(2)(tben)(2)](ClO4)(2) (2; tben = di-(t)butylethylenediamine) and [Cu-2(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 similar to 0.9 GPa for 1, 2 and 3: the exchange becomes less antiferromagnetic in 1 and 2 and more ferromagnetic in 3.

Original languageEnglish
Pages (from-to)113-123
Number of pages11
JournalDalton Transactions
Volume39
Issue number1
DOIs
Publication statusPublished - 2010
Externally publishedYes

Cite this

Prescimone, A., Sanchez-Benitez, J., Kamenev, K. K., Moggach, S. A., Warren, J. E., Lennie, A. R., Murrie, M., Parsons, S., & Brechin, E. K. (2010). High pressure studies of hydroxo-bridged Cu(II) dimers. Dalton Transactions, 39(1), 113-123. https://doi.org/10.1039/b918287j