Spin-singlet transition in the magnetic hybrid compound from a spin-crossover Fe(III) cation and π-radical anion

Kazuyuki Takahashi; Takahiro Sakurai; Wei Min Zhang; Susumu Okubo; Hitoshi Ohta; Takashi Yamamoto; Yasuaki Einaga; Hatsumi Mori

doi:10.3390/inorganics5030054

Spin-singlet transition in the magnetic hybrid compound from a spin-crossover Fe(III) cation and π-radical anion

Kazuyuki Takahashi, Takahiro Sakurai, Wei Min Zhang, Susumu Okubo, Hitoshi Ohta, Takashi Yamamoto, Yasuaki Einaga, Hatsumi Mori

Department of Chemistry

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

5 Citations (Scopus)

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.

Original language	English
Article number	54
Journal	Inorganics
Volume	5
Issue number	3
DOIs	https://doi.org/10.3390/inorganics5030054
Publication status	Published - 2017 Sept 1

Keywords

Fe(III) complex
Magnetic correlation
Ni dithiolene complex
Spin transition
Spin-crossover
Spin-singlet formation
π-radical
π-stacking interaction

ASJC Scopus subject areas

Inorganic Chemistry

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title = "Spin-singlet transition in the magnetic hybrid compound from a spin-crossover Fe(III) cation and π-radical anion",

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 M{\"o}ssbauer 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.",

keywords = "Fe(III) complex, Magnetic correlation, Ni dithiolene complex, Spin transition, Spin-crossover, Spin-singlet formation, π-radical, π-stacking interaction",

author = "Kazuyuki Takahashi and Takahiro Sakurai and Zhang, {Wei Min} and Susumu Okubo and Hitoshi Ohta and Takashi Yamamoto and Yasuaki Einaga and Hatsumi Mori",

note = "Publisher Copyright: {\textcopyright} 2017 by the authors.",

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language = "English",

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T1 - Spin-singlet transition in the magnetic hybrid compound from a spin-crossover Fe(III) cation and π-radical anion

AU - Takahashi, Kazuyuki

AU - Sakurai, Takahiro

AU - Zhang, Wei Min

AU - Okubo, Susumu

AU - Ohta, Hitoshi

AU - Yamamoto, Takashi

AU - Einaga, Yasuaki

AU - Mori, Hatsumi

PY - 2017/9/1

Y1 - 2017/9/1

N2 - 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.

AB - 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.

KW - Fe(III) complex

KW - Magnetic correlation

KW - Ni dithiolene complex

KW - Spin transition

KW - Spin-crossover

KW - Spin-singlet formation

KW - π-radical

KW - π-stacking interaction

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Spin-singlet transition in the magnetic hybrid compound from a spin-crossover Fe(III) cation and π-radical anion

Abstract

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