High-Pressure Study of Oxo-bridged Mixed-Valent Mn-III/Mn-IV Dimers

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

Research output: Contribution to journalArticlepeer-review

Abstract / Description of output

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. [Mn2O2(bpy)(4)](ClO4)(3)center dot 3CH(3)CN, (1.3CH(3)CN; bpy = 2,2'-bipyridine) has been compressed to 2.0 GPa whilst [Mn2O2(bpy)(4)](PF6)(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 PF6 salt of [Mn2O2(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.

Original languageEnglish
Pages (from-to)221-230
Number of pages10
JournalZeitschrift für Naturforschung B
Volume65
Issue number3
Publication statusPublished - Mar 2010

Keywords / Materials (for Non-textual outputs)

  • High Pressure
  • Coordination Chemistry
  • Clusters
  • X-Ray Crystallography
  • SQUID Magnetometry
  • X-RAY-DIFFRACTION
  • INELASTIC NEUTRON-SCATTERING
  • TRANSITION-METAL-COMPLEXES
  • DIAMOND-ANVIL CELL
  • CRYSTAL-STRUCTURES
  • MAGNETOSTRUCTURAL CORRELATIONS
  • MANGANESE COMPLEXES
  • MAGNETIC-PROPERTIES
  • LOW-TEMPERATURE
  • ANISOTROPY

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