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New spin-crossover compounds containing the [ni(Mnt)] anion (mnt = maleonitriledithiolate)

New spin-crossover compounds containing the [ni(Mnt)] anion (mnt = maleonitriledithiolate)
New spin-crossover compounds containing the [ni(Mnt)] anion (mnt = maleonitriledithiolate)

Two novel salts containing the anion [Ni(mnt)2 ] (mnt = maleonitriledithiolate) have been synthesized. The counter-ions, [Fe(II)(L1 or L2)2 ], are cationic complexes where L1 and L2 are methylated derivatives of 2,6-bis(pyazolyl)pyridine or pyrazine, which are similar to ligands found in a series of spin-crossover (SCO) complexes. Both salts are characterized by variable temperature single crystal X-ray diffraction and bulk magnetization measurements. Compound 1, [Fe(II)(L1)2][Ni(mnt)2]2 displays an incomplete and gradual SCO up to 300 K, followed by a more rapid increase in the high-spin fraction between 300 and 350 K. Compound 2, [Fe(II)(L2)2 ][Ni(mnt)2 ]2.MeNO2, shows a gradual, but more complete SCO response centered at 250 K. For compound 2, the SCO is confirmed by variable temperature Mössbauer spectroscopy. In both cases, the anionic moieties are isolated from each other and so no electrical conductivity is observed.

Magnetic materials, Molecular magnets, Molecular materials, Spin-crossover
72
Turner, Scott S.
dff25cc2-54a4-4c11-9621-fbe854931843
Daniell, Joanna
d682e5f4-3ad4-41c5-a8af-bdeab4c6075b
Akutsu, Hiroki
86a57ad8-7b6f-4df2-be69-25b1c08d9a6c
Horton, Peter N.
154c8930-bfc3-495b-ad4a-8a278d5da3a5
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Schünemann, Volker
6278b78f-3ffa-4d64-8b96-1b921c2f50b7
Turner, Scott S.
dff25cc2-54a4-4c11-9621-fbe854931843
Daniell, Joanna
d682e5f4-3ad4-41c5-a8af-bdeab4c6075b
Akutsu, Hiroki
86a57ad8-7b6f-4df2-be69-25b1c08d9a6c
Horton, Peter N.
154c8930-bfc3-495b-ad4a-8a278d5da3a5
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Schünemann, Volker
6278b78f-3ffa-4d64-8b96-1b921c2f50b7

Turner, Scott S., Daniell, Joanna, Akutsu, Hiroki, Horton, Peter N., Coles, Simon J. and Schünemann, Volker (2021) New spin-crossover compounds containing the [ni(Mnt)] anion (mnt = maleonitriledithiolate). Magnetochemistry, 7 (5), 72. (doi:10.3390/magnetochemistry7050072).

Record type: Article

Abstract

Two novel salts containing the anion [Ni(mnt)2 ] (mnt = maleonitriledithiolate) have been synthesized. The counter-ions, [Fe(II)(L1 or L2)2 ], are cationic complexes where L1 and L2 are methylated derivatives of 2,6-bis(pyazolyl)pyridine or pyrazine, which are similar to ligands found in a series of spin-crossover (SCO) complexes. Both salts are characterized by variable temperature single crystal X-ray diffraction and bulk magnetization measurements. Compound 1, [Fe(II)(L1)2][Ni(mnt)2]2 displays an incomplete and gradual SCO up to 300 K, followed by a more rapid increase in the high-spin fraction between 300 and 350 K. Compound 2, [Fe(II)(L2)2 ][Ni(mnt)2 ]2.MeNO2, shows a gradual, but more complete SCO response centered at 250 K. For compound 2, the SCO is confirmed by variable temperature Mössbauer spectroscopy. In both cases, the anionic moieties are isolated from each other and so no electrical conductivity is observed.

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Accepted/In Press date: 14 May 2021
Published date: 19 May 2021
Additional Information: Funding Information: V.S. acknowledges the support of the research initiative NANOKAT. The PhD studies of J.D. were supported by the University of Surrey and EPSRC. Publisher Copyright: © 2021 by the authors. Licensee MDPI, Basel, Switzerland. Copyright: Copyright 2021 Elsevier B.V., All rights reserved.
Keywords: Magnetic materials, Molecular magnets, Molecular materials, Spin-crossover

Identifiers

Local EPrints ID: 449908
URI: http://eprints.soton.ac.uk/id/eprint/449908
PURE UUID: b6f9b0f8-c403-4d1a-ac31-0ff1b818906f
ORCID for Peter N. Horton: ORCID iD orcid.org/0000-0001-8886-2016
ORCID for Simon J. Coles: ORCID iD orcid.org/0000-0001-8414-9272

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Date deposited: 24 Jun 2021 16:32
Last modified: 25 Jun 2021 01:36

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Contributors

Author: Scott S. Turner
Author: Joanna Daniell
Author: Hiroki Akutsu
Author: Peter N. Horton ORCID iD
Author: Simon J. Coles ORCID iD
Author: Volker Schünemann

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