Publication

High-Pressure Study of Oxo-bridged Mixed-Valent Mn(III)/Mn(IV) 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 V. Kamenev (School of Engineering and Centre for Science at Extreme Conditions, The University of Edinburgh, U.K.) , 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: Zeitschrift Fur Naturforschung Section B-a Journal Of Chemical Sciences , VOL 65 (3)

State: Published (Approved)
Published: March 2010

Abstract: A combination of high-pressure single crystal X-ray diffraction and high-pressure SQUID magnetometry has been used to study two oxo-bridged mixed-valent Mn(III)/Mn(IV) dimers. [Mn(2)O(2)(bpy)(4)](ClO(4))(3)center dot 3CH(3)CN, (1.3CH(3)CN; bpy = 2,2'-bipyridine) has been compressed to 2.0 GPa whilst [Mn(2)O(2)(bpy)(4)](PF(6))(3)center dot 2CH(3)CN center dot 1H(2)O, (2.2CH(3)CN center dot 1H(2)O) could be measured crystallographically up to 4.55 GPa. The PF(6) salt of [Mn(2)O(2)(bpy)(4)](3+) has never been reported before while 1 has been reported as a hydrate and in a different crystallographic space group. The application of hydrostatic pressure imposes significant distortions and modifications in the structures of both complexes. In particular, in complex 1.3CH(3)CN the Mn-Mn separation is reduced by the contraction of some of the Mn-O bond lengths, whilst in 2.2CH(3)CN center dot 1H(2)O the Mn-O Mn bridging angles and the Mn-O bond lengths are substantially unchanged. Interestingly 2.2CH(3)CN center dot 1H(2)O also shows a constant contraction in nearly all the Mn-N bonds. The magnetic behaviour of the complexes has been measured up to 0.87 GPa for 1.3CH(3)CN and 0.84 GPa for 2.2CH(3)CN center dot 1H(2)O.

Journal Keywords: High Pressure; Coordination Chemistry; Clusters; X-Ray Crystallography; Squid Magnetometry

Subject Areas: Chemistry

Facility: Daresbury Laboratory, U.K.

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