Modification of spin crossover behavior through solvent assisted formation and solvent inclusion in a triply interpenetrating three-dimensional network

Matthias Bartel; Alina Absmeier; Guy N.L. Jameson; Franz Werner; Kenichi Kato; Masaki Takata; Roman Boca; Miki Hasegawa; Kurt Mereiter; Andrea Caneschi; Wolfgang Linert

doi:10.1021/ic070173q

Modification of spin crossover behavior through solvent assisted formation and solvent inclusion in a triply interpenetrating three-dimensional network

Matthias Bartel, Alina Absmeier, Guy N.L. Jameson, Franz Werner, Kenichi Kato, Masaki Takata, Roman Boca, Miki Hasegawa, Kurt Mereiter, Andrea Caneschi, Wolfgang Linert

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

45 Citations (Scopus)

Abstract

The 3D coordination polymer [Fe(4ditz)₃](PF₆) ₂·Solv consists of three interpenetrating infinite networks. There are cavities between iron atoms of different networks, which are partly filled with solvent molecules. With a change of the solvent used during synthesis from methanol to ethanol, the magnetic behavior of the materials changes. Both show an abrupt two-step spin crossover from low spin (S = 0) to high spin (S = 2) with the methanolate curve lying 7 K higher and showing a small hysteresis. Single crystal and powder diffraction studies show that they both have the same structure, but in powder form, the methanolate slowly loses methanol to finally leave about 0.075 MeOH/Fe. In comparison, the bigger ethanol remains at 0.25 EtOH/Fe. These results, in conjunction with thermodynamic data, strongly suggest that the differences in magnetic behavior are largely entropic in nature. Possible reasons for this are discussed.

Original language	English
Pages (from-to)	4220-4229
Number of pages	10
Journal	Inorganic chemistry
Volume	46
Issue number	10
DOIs	https://doi.org/10.1021/ic070173q
Publication status	Published - 2007 May 14
Externally published	Yes

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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Bartel, M., Absmeier, A., Jameson, G. N. L., Werner, F., Kato, K., Takata, M., Boca, R., Hasegawa, M., Mereiter, K., Caneschi, A., & Linert, W. (2007). Modification of spin crossover behavior through solvent assisted formation and solvent inclusion in a triply interpenetrating three-dimensional network. Inorganic chemistry, 46(10), 4220-4229. https://doi.org/10.1021/ic070173q

Bartel, M, Absmeier, A, Jameson, GNL, Werner, F, Kato, K, Takata, M, Boca, R, Hasegawa, M, Mereiter, K, Caneschi, A & Linert, W 2007, 'Modification of spin crossover behavior through solvent assisted formation and solvent inclusion in a triply interpenetrating three-dimensional network', Inorganic chemistry, vol. 46, no. 10, pp. 4220-4229. https://doi.org/10.1021/ic070173q

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abstract = "The 3D coordination polymer [Fe(4ditz)3](PF6) 2·Solv consists of three interpenetrating infinite networks. There are cavities between iron atoms of different networks, which are partly filled with solvent molecules. With a change of the solvent used during synthesis from methanol to ethanol, the magnetic behavior of the materials changes. Both show an abrupt two-step spin crossover from low spin (S = 0) to high spin (S = 2) with the methanolate curve lying 7 K higher and showing a small hysteresis. Single crystal and powder diffraction studies show that they both have the same structure, but in powder form, the methanolate slowly loses methanol to finally leave about 0.075 MeOH/Fe. In comparison, the bigger ethanol remains at 0.25 EtOH/Fe. These results, in conjunction with thermodynamic data, strongly suggest that the differences in magnetic behavior are largely entropic in nature. Possible reasons for this are discussed.",

author = "Matthias Bartel and Alina Absmeier and Jameson, {Guy N.L.} and Franz Werner and Kenichi Kato and Masaki Takata and Roman Boca and Miki Hasegawa and Kurt Mereiter and Andrea Caneschi and Wolfgang Linert",

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AU - Bartel, Matthias

AU - Absmeier, Alina

AU - Jameson, Guy N.L.

AU - Werner, Franz

AU - Kato, Kenichi

AU - Takata, Masaki

AU - Boca, Roman

AU - Hasegawa, Miki

AU - Mereiter, Kurt

AU - Caneschi, Andrea

AU - Linert, Wolfgang

PY - 2007/5/14

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N2 - The 3D coordination polymer [Fe(4ditz)3](PF6) 2·Solv consists of three interpenetrating infinite networks. There are cavities between iron atoms of different networks, which are partly filled with solvent molecules. With a change of the solvent used during synthesis from methanol to ethanol, the magnetic behavior of the materials changes. Both show an abrupt two-step spin crossover from low spin (S = 0) to high spin (S = 2) with the methanolate curve lying 7 K higher and showing a small hysteresis. Single crystal and powder diffraction studies show that they both have the same structure, but in powder form, the methanolate slowly loses methanol to finally leave about 0.075 MeOH/Fe. In comparison, the bigger ethanol remains at 0.25 EtOH/Fe. These results, in conjunction with thermodynamic data, strongly suggest that the differences in magnetic behavior are largely entropic in nature. Possible reasons for this are discussed.

AB - The 3D coordination polymer [Fe(4ditz)3](PF6) 2·Solv consists of three interpenetrating infinite networks. There are cavities between iron atoms of different networks, which are partly filled with solvent molecules. With a change of the solvent used during synthesis from methanol to ethanol, the magnetic behavior of the materials changes. Both show an abrupt two-step spin crossover from low spin (S = 0) to high spin (S = 2) with the methanolate curve lying 7 K higher and showing a small hysteresis. Single crystal and powder diffraction studies show that they both have the same structure, but in powder form, the methanolate slowly loses methanol to finally leave about 0.075 MeOH/Fe. In comparison, the bigger ethanol remains at 0.25 EtOH/Fe. These results, in conjunction with thermodynamic data, strongly suggest that the differences in magnetic behavior are largely entropic in nature. Possible reasons for this are discussed.

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Modification of spin crossover behavior through solvent assisted formation and solvent inclusion in a triply interpenetrating three-dimensional network

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