Cooperative high-temperature spin crossover accompanied by a highly anisotropic structural distortion

Il'ya A. Gural'skiy; Bohdan O. Golub; Sergii I. Shylin; Vadim Ksenofontov; Helena J. Shepherd; Paul R. Raithby; Wolfgang Tremel; Igor O. Fritsky

doi:10.1002/ejic.201600406

Cooperative high-temperature spin crossover accompanied by a highly anisotropic structural distortion

Il'ya A. Gural'skiy, Bohdan O. Golub, Sergii I. Shylin, Vadim Ksenofontov, Helena J. Shepherd, Paul R. Raithby, Wolfgang Tremel, Igor O. Fritsky

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Abstract

Spin transitions are a spectacular example of molecular switching that can provoke extreme electronic and structural reorganizations in coordination compounds. A new 3D cyanoheterometallic framework, [Fe(pz)(Au(CN)₂)₂], has been synthesized in which a highly cooperative spin crossover has been observed at 367 and 349 K in heating and cooling modes, respectively. Mössbauer spectroscopy revealed a complete transition between the diamagnetic and paramagnetic states of the iron centres. The low-spin-to-high-spin transition induced a drastic structural distortion involving a large one-directional expansion (ca. 10.6%) and contraction (ca. 9.6%) of the lattice. Negative thermal expansion along the c axis was detected below and above the transition temperature.

Original language	English
Pages (from-to)	3191-3195
Journal	European Journal of Inorganic Chemistry
Volume	2016
Issue number	19
Early online date	19 May 2016
DOIs	https://doi.org/10.1002/ejic.201600406
Publication status	Published - Jul 2016

Keywords

Cooperative effects
Iron
Magnetic properties
Metal-organic frameworks
Spin crossover

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10.1002/ejic.201600406

EJIC
This is the peer reviewed version of the following article: Il'ya A. Gural'skiy Bohdan O. Golub Sergii I. Shylin Vadim Ksenofontov Helena J. Shepherd Paul R. Raithby Wolfgang Tremel Igor O. Fritsky (2016) Cooperative High‐Temperature Spin Crossover Accompanied by a Highly Anisotropic Structural Distortion. European Journal of Inorganic Chemistry, 2016(19) which has been published in final form at 10.1002/ejic.201600406. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving.
Accepted author manuscript, 1.28 MB

http://dx.doi.org/10.1002/ejic.201600406

Cite this

@article{8016cb60fc564c4280b8078f845ab283,

title = "Cooperative high-temperature spin crossover accompanied by a highly anisotropic structural distortion",

abstract = "Spin transitions are a spectacular example of molecular switching that can provoke extreme electronic and structural reorganizations in coordination compounds. A new 3D cyanoheterometallic framework, [Fe(pz)(Au(CN)2)2], has been synthesized in which a highly cooperative spin crossover has been observed at 367 and 349 K in heating and cooling modes, respectively. M{\"o}ssbauer spectroscopy revealed a complete transition between the diamagnetic and paramagnetic states of the iron centres. The low-spin-to-high-spin transition induced a drastic structural distortion involving a large one-directional expansion (ca. 10.6%) and contraction (ca. 9.6%) of the lattice. Negative thermal expansion along the c axis was detected below and above the transition temperature.",

keywords = "Cooperative effects, Iron, Magnetic properties, Metal-organic frameworks, Spin crossover",

author = "Gural'skiy, {Il'ya A.} and Golub, {Bohdan O.} and Shylin, {Sergii I.} and Vadim Ksenofontov and Shepherd, {Helena J.} and Raithby, {Paul R.} and Wolfgang Tremel and Fritsky, {Igor O.}",

year = "2016",

month = jul,

doi = "10.1002/ejic.201600406",

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volume = "2016",

pages = "3191--3195",

journal = "European Journal of Inorganic Chemistry",

issn = "1434-1948",

publisher = "Wiley-VCH Verlag",

number = "19",

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TY - JOUR

T1 - Cooperative high-temperature spin crossover accompanied by a highly anisotropic structural distortion

AU - Gural'skiy, Il'ya A.

AU - Golub, Bohdan O.

AU - Shylin, Sergii I.

AU - Ksenofontov, Vadim

AU - Shepherd, Helena J.

AU - Raithby, Paul R.

AU - Tremel, Wolfgang

AU - Fritsky, Igor O.

PY - 2016/7

Y1 - 2016/7

N2 - Spin transitions are a spectacular example of molecular switching that can provoke extreme electronic and structural reorganizations in coordination compounds. A new 3D cyanoheterometallic framework, [Fe(pz)(Au(CN)2)2], has been synthesized in which a highly cooperative spin crossover has been observed at 367 and 349 K in heating and cooling modes, respectively. Mössbauer spectroscopy revealed a complete transition between the diamagnetic and paramagnetic states of the iron centres. The low-spin-to-high-spin transition induced a drastic structural distortion involving a large one-directional expansion (ca. 10.6%) and contraction (ca. 9.6%) of the lattice. Negative thermal expansion along the c axis was detected below and above the transition temperature.

AB - Spin transitions are a spectacular example of molecular switching that can provoke extreme electronic and structural reorganizations in coordination compounds. A new 3D cyanoheterometallic framework, [Fe(pz)(Au(CN)2)2], has been synthesized in which a highly cooperative spin crossover has been observed at 367 and 349 K in heating and cooling modes, respectively. Mössbauer spectroscopy revealed a complete transition between the diamagnetic and paramagnetic states of the iron centres. The low-spin-to-high-spin transition induced a drastic structural distortion involving a large one-directional expansion (ca. 10.6%) and contraction (ca. 9.6%) of the lattice. Negative thermal expansion along the c axis was detected below and above the transition temperature.

KW - Cooperative effects

KW - Iron

KW - Magnetic properties

KW - Metal-organic frameworks

KW - Spin crossover

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UR - http://dx.doi.org/10.1002/ejic.201600406

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DO - 10.1002/ejic.201600406

M3 - Article

AN - SCOPUS:84971445003

SN - 1434-1948

VL - 2016

SP - 3191

EP - 3195

JO - European Journal of Inorganic Chemistry

JF - European Journal of Inorganic Chemistry

IS - 19

ER -

Cooperative high-temperature spin crossover accompanied by a highly anisotropic structural distortion

Abstract

Keywords

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Understanding and Engineering Function in Switchable Molecular Crystals

Dual source (Cu and Mo) Single Crystal Diffractometer (SuperNova)

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Cooperative high-temperature spin crossover accompanied by a highly anisotropic structural distortion

Abstract

Keywords

Access to Document

Other files and links

Fingerprint

Projects

Understanding and Engineering Function in Switchable Molecular Crystals

Equipment

Dual source (Cu and Mo) Single Crystal Diffractometer (SuperNova)

Cite this