Thermal low spinhigh spin equilibrium of Fe(II) in thiospinels CuFe 0.5(Sn(1-x)Tix)1.5S4 (0≤x≤1)

M. Womes; C. Reibel; A. Mari; D. Zitoun

doi:10.1016/j.jssc.2011.01.038

Thermal low spinhigh spin equilibrium of Fe(II) in thiospinels CuFe _0.5(Sn_(1-x)Ti_x)_1.5S₄ (0≤x≤1)

M. Womes, C. Reibel, A. Mari, D. Zitoun

Department of Chemistry

Bar-Ilan University

Research output: Contribution to journal › Article › peer-review

Abstract

A series of spinel compounds with composition CuFe_0.5(Sn _(1-x)Ti_x)_1.5S₄ (0≤x≤1) is analysed by X-ray diffraction, measurements of magnetic susceptibilities and ⁵⁷Fe Mössbauer spectroscopy. All samples show a temperature-dependent equilibrium between an electronic low spin 3d(t _2g)⁶(e_g)⁰ and a high spin 3d(t _2g)⁴(e_g)² state of the Fe(II) ions. The spin crossover is of the continuous type and extends over several hundred degrees in all samples. The Sn/Ti ratio influences the thermal equilibrium between the two spin states. Substitution of Sn(IV) by the smaller Ti(IV) ions leads to a more compact crystal lattice, which, in contrast to many metalorganic Fe(II) complexes, does not stabilise the low spin state, but increases the residual high spin fraction for T→0 K. The role played by antiferromagnetic spin coupling in the stabilisation of the high spin state is discussed. The results are compared with model calculations treating the effect of magnetic interactions on spin state equilibria.

Original language	English
Pages (from-to)	753-763
Number of pages	11
Journal	Journal of Solid State Chemistry
Volume	184
Issue number	4
DOIs	https://doi.org/10.1016/j.jssc.2011.01.038
State	Published - Apr 2011

Keywords

Exchange interaction
Magnetic properties
Mössbauer spectroscopy
Spin crossover
Spinel lattice

All Science Journal Classification (ASJC) codes

Electronic, Optical and Magnetic Materials
Ceramics and Composites
Condensed Matter Physics
Physical and Theoretical Chemistry
Inorganic Chemistry
Materials Chemistry

Access to Document

10.1016/j.jssc.2011.01.038

Cite this

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title = "Thermal low spinhigh spin equilibrium of Fe(II) in thiospinels CuFe 0.5(Sn(1-x)Tix)1.5S4 (0≤x≤1)",

abstract = "A series of spinel compounds with composition CuFe0.5(Sn (1-x)Tix)1.5S4 (0≤x≤1) is analysed by X-ray diffraction, measurements of magnetic susceptibilities and 57Fe M{\"o}ssbauer spectroscopy. All samples show a temperature-dependent equilibrium between an electronic low spin 3d(t 2g)6(eg)0 and a high spin 3d(t 2g)4(eg)2 state of the Fe(II) ions. The spin crossover is of the continuous type and extends over several hundred degrees in all samples. The Sn/Ti ratio influences the thermal equilibrium between the two spin states. Substitution of Sn(IV) by the smaller Ti(IV) ions leads to a more compact crystal lattice, which, in contrast to many metalorganic Fe(II) complexes, does not stabilise the low spin state, but increases the residual high spin fraction for T→0 K. The role played by antiferromagnetic spin coupling in the stabilisation of the high spin state is discussed. The results are compared with model calculations treating the effect of magnetic interactions on spin state equilibria.",

keywords = "Exchange interaction, Magnetic properties, M{\"o}ssbauer spectroscopy, Spin crossover, Spinel lattice",

author = "M. Womes and C. Reibel and A. Mari and D. Zitoun",

year = "2011",

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doi = "10.1016/j.jssc.2011.01.038",

language = "الإنجليزيّة",

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T1 - Thermal low spinhigh spin equilibrium of Fe(II) in thiospinels CuFe 0.5(Sn(1-x)Tix)1.5S4 (0≤x≤1)

AU - Womes, M.

AU - Reibel, C.

AU - Mari, A.

AU - Zitoun, D.

PY - 2011/4

Y1 - 2011/4

N2 - A series of spinel compounds with composition CuFe0.5(Sn (1-x)Tix)1.5S4 (0≤x≤1) is analysed by X-ray diffraction, measurements of magnetic susceptibilities and 57Fe Mössbauer spectroscopy. All samples show a temperature-dependent equilibrium between an electronic low spin 3d(t 2g)6(eg)0 and a high spin 3d(t 2g)4(eg)2 state of the Fe(II) ions. The spin crossover is of the continuous type and extends over several hundred degrees in all samples. The Sn/Ti ratio influences the thermal equilibrium between the two spin states. Substitution of Sn(IV) by the smaller Ti(IV) ions leads to a more compact crystal lattice, which, in contrast to many metalorganic Fe(II) complexes, does not stabilise the low spin state, but increases the residual high spin fraction for T→0 K. The role played by antiferromagnetic spin coupling in the stabilisation of the high spin state is discussed. The results are compared with model calculations treating the effect of magnetic interactions on spin state equilibria.

AB - A series of spinel compounds with composition CuFe0.5(Sn (1-x)Tix)1.5S4 (0≤x≤1) is analysed by X-ray diffraction, measurements of magnetic susceptibilities and 57Fe Mössbauer spectroscopy. All samples show a temperature-dependent equilibrium between an electronic low spin 3d(t 2g)6(eg)0 and a high spin 3d(t 2g)4(eg)2 state of the Fe(II) ions. The spin crossover is of the continuous type and extends over several hundred degrees in all samples. The Sn/Ti ratio influences the thermal equilibrium between the two spin states. Substitution of Sn(IV) by the smaller Ti(IV) ions leads to a more compact crystal lattice, which, in contrast to many metalorganic Fe(II) complexes, does not stabilise the low spin state, but increases the residual high spin fraction for T→0 K. The role played by antiferromagnetic spin coupling in the stabilisation of the high spin state is discussed. The results are compared with model calculations treating the effect of magnetic interactions on spin state equilibria.

KW - Exchange interaction

KW - Magnetic properties

KW - Mössbauer spectroscopy

KW - Spin crossover

KW - Spinel lattice

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