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Inorganics 2017, 5(3), 54; https://doi.org/10.3390/inorganics5030054

Spin-Singlet Transition in the Magnetic Hybrid Compound from a Spin-Crossover Fe(III) Cation and π-Radical Anion

1
Department of Chemistry, Graduate School of Science, Kobe University, 1-1 Rokkodai-cho, Nada-ku, Kobe, Hyogo 657-8501, Japan
2
Research Facility Center for Science and Technology, Kobe University, 1-1 Rokkodai-cho, Nada-ku, Kobe, Hyogo 657-8501, Japan
3
Molecular Photoscience Research Center, Kobe University, 1-1 Rokkodai-cho, Nada-ku, Kobe, Hyogo 657-8501, Japan
4
Department of Chemistry, Graduate School of Science and Technology, Keio University, 3-14-1 Hiyoshi, Kohoku-ku, Yokohama, Kanagawa 223-8522, Japan
5
Institute for Solid State Physics, The University of Tokyo, 5-1-5 Kashiwanoha, Kashiwa, Chiba 277-8581, Japan
*
Author to whom correspondence should be addressed.
Received: 5 July 2017 / Revised: 3 August 2017 / Accepted: 11 August 2017 / Published: 16 August 2017
(This article belongs to the Special Issue Spin-Crossover Complexes)
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Abstract

To develop a new spin-crossover functional material, a magnetic hybrid compound [Fe(qsal)2][Ni(mnt)2] was designed and synthesized (Hqsal = N-(8-quinolyl)salicylaldimine, mnt = maleonitriledithiolate). The temperature dependence of magnetic susceptibility suggested the coexistence of the high-spin (HS) Fe(III) cation and π-radical anion at room temperature and a magnetic transition below 100 K. The thermal variation of crystal structures revealed that strong π-stacking interaction between the π-ligand in the [Fe(qsal)2] cation and [Ni(mnt)2] anion induced the distortion of an Fe(III) coordination structure and the suppression of a dimerization of the [Ni(mnt)2] anion. Transfer integral calculations indicated that the magnetic transition below 100 K originated from a spin-singlet formation transformation in the [Ni(mnt)2] dimer. The magnetic relaxation of Mössbauer spectra and large thermal variation of a g-value in electron paramagnetic resonance spectra below the magnetic transition temperature implied the existence of a magnetic correlation between d-spin and π-spin. View Full-Text
Keywords: spin-crossover; π-radical; spin transition; spin-singlet formation; π-stacking interaction; magnetic correlation; Fe(III) complex; Ni dithiolene complex spin-crossover; π-radical; spin transition; spin-singlet formation; π-stacking interaction; magnetic correlation; Fe(III) complex; Ni dithiolene complex
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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. (CC BY 4.0).

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Takahashi, K.; Sakurai, T.; Zhang, W.-M.; Okubo, S.; Ohta, H.; Yamamoto, T.; Einaga, Y.; Mori, H. Spin-Singlet Transition in the Magnetic Hybrid Compound from a Spin-Crossover Fe(III) Cation and π-Radical Anion. Inorganics 2017, 5, 54.

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