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

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 journal › Article › peer-review

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. [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 language	English
Pages (from-to)	221-230
Number of pages	10
Journal	Zeitschrift für Naturforschung B
Volume	65
Issue number	3
Publication status	Published - 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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High-Pressure Study of Oxo-bridged Mixed-Valent MnIII_MnIV Dimers
Copyright © 2010 Verlag der Zeitschrift fur Naturforschung, Tubingen. All rights reserved.
Final published version, 3.2 MB

EPR characterization of molecular magneto-structural correlations under pressure
Brechin, E. (Principal Investigator), Kamenev, K. (Co-investigator) & Parsons, S. (Co-investigator)
EPSRC
1/10/09 → 31/12/12
Project: Research
A new SQUID magnetometer for extreme conditions research
Kamenev, K. (Principal Investigator), Attfield, P. (Co-investigator), Bos, J.-W. (Co-investigator), Brechin, E. (Co-investigator), Harrison, A. (Co-investigator) & Huxley, A. (Co-investigator)
EPSRC
1/09/07 → 31/01/11
Project: Research
Effect of High Pressure on Single Molecule Magnets
Kamenev, K. (Principal Investigator), Allan, D. (Co-investigator), Brechin, E. (Co-investigator), Harrison, A. (Co-investigator) & Parsons, S. (Co-investigator)
EPSRC
1/01/06 → 30/04/09
Project: Research

Cite this

@article{43b64dcf901c4781b73fe4aa3a2e9c40,

title = "High-Pressure Study of Oxo-bridged Mixed-Valent Mn-III/Mn-IV Dimers",

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. [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.",

keywords = "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",

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

year = "2010",

month = mar,

language = "English",

volume = "65",

pages = "221--230",

journal = "Zeitschrift f{\"u}r Naturforschung B",

issn = "0932-0776",

publisher = "De Gruyter",

number = "3",

}

TY - JOUR

T1 - High-Pressure Study of Oxo-bridged Mixed-Valent Mn-III/Mn-IV Dimers

AU - Prescimone, Alessandro

AU - Sanchez-Benitez, Javier

AU - Kamenev, Konstantin V.

AU - Warren, John E.

AU - Lennie, Alistair R.

AU - Murrie, Mark

AU - Parsons, Simon

AU - Brechin, Euan K.

PY - 2010/3

Y1 - 2010/3

N2 - 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.

AB - 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.

KW - High Pressure

KW - Coordination Chemistry

KW - Clusters

KW - X-Ray Crystallography

KW - SQUID Magnetometry

KW - X-RAY-DIFFRACTION

KW - INELASTIC NEUTRON-SCATTERING

KW - TRANSITION-METAL-COMPLEXES

KW - DIAMOND-ANVIL CELL

KW - CRYSTAL-STRUCTURES

KW - MAGNETOSTRUCTURAL CORRELATIONS

KW - MANGANESE COMPLEXES

KW - MAGNETIC-PROPERTIES

KW - LOW-TEMPERATURE

KW - ANISOTROPY

M3 - Article

SN - 0932-0776

VL - 65

SP - 221

EP - 230

JO - Zeitschrift für Naturforschung B

JF - Zeitschrift für Naturforschung B

IS - 3

ER -

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

Abstract

Keywords / Materials (for Non-textual outputs)

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Projects

EPR characterization of molecular magneto-structural correlations under pressure

A new SQUID magnetometer for extreme conditions research

Effect of High Pressure on Single Molecule Magnets

Cite this