Novel Fe(II) spin crossover complexes involving a chalcogen-bond and π-stacking interactions with a paramagnetic and nonmagnetic M(dmit)<inf>2</inf> anion (M = Ni, Au; Dmit = 4,5-dithiolato-1,3-dithiole-2-thione)

Mitsunobu Okai, Kazuyuki Takahashi, Takahiro Sakurai, Hitoshi Ohta, Takashi Yamamoto, Yasuaki Einaga

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6 Citations (Scopus)

Abstract

To introduce both an inter-sulphur atom and π-stacking interaction between a spin crossover (SCO) cation and paramagnetic anion, we designed and synthesised two novel Fe(ii) SCO compounds involving a terpyridine-type thiazole containing ligand with the paramagnetic Ni(dmit)<inf>2</inf> and nonmagnetic Au(dmit)<inf>2</inf> anion (dmit = 4,5-dithiolato-1,3-dithiole-2-thione). The temperature variations of magnetic susceptibility and Mössbauer spectroscopy revealed that both complexes exhibited an almost complete SCO conversion, and moreover, the Ni(dmit)<inf>2</inf> anion was in a paramagnetic state down to 2 K. The crystal structures for the Ni(dmit)<inf>2</inf> complex at 213 and 400 K indicated that the chalcogen-bond and π-stacking interaction would be enhanced by the electrostatic interaction between the cation and anion, preventing the π-radicals from dimerising. The light-induced excited spin state trapping effect was observed at 5 K.

Original languageEnglish
Pages (from-to)7858-7864
Number of pages7
JournalJournal of Materials Chemistry C
Volume3
Issue number30
DOIs
Publication statusPublished - 2015 Aug 14

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Chalcogens
Thiones
Anions
Negative ions
Cations
Positive ions
Thiazoles
Coulomb interactions
Magnetic susceptibility
Sulfur
Crystal structure
Ligands
Spectroscopy
Atoms

ASJC Scopus subject areas

  • Chemistry(all)
  • Materials Chemistry

Cite this

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title = "Novel Fe(II) spin crossover complexes involving a chalcogen-bond and π-stacking interactions with a paramagnetic and nonmagnetic M(dmit)2 anion (M = Ni, Au; Dmit = 4,5-dithiolato-1,3-dithiole-2-thione)",
abstract = "To introduce both an inter-sulphur atom and π-stacking interaction between a spin crossover (SCO) cation and paramagnetic anion, we designed and synthesised two novel Fe(ii) SCO compounds involving a terpyridine-type thiazole containing ligand with the paramagnetic Ni(dmit)2 and nonmagnetic Au(dmit)2 anion (dmit = 4,5-dithiolato-1,3-dithiole-2-thione). The temperature variations of magnetic susceptibility and M{\"o}ssbauer spectroscopy revealed that both complexes exhibited an almost complete SCO conversion, and moreover, the Ni(dmit)2 anion was in a paramagnetic state down to 2 K. The crystal structures for the Ni(dmit)2 complex at 213 and 400 K indicated that the chalcogen-bond and π-stacking interaction would be enhanced by the electrostatic interaction between the cation and anion, preventing the π-radicals from dimerising. The light-induced excited spin state trapping effect was observed at 5 K.",
author = "Mitsunobu Okai and Kazuyuki Takahashi and Takahiro Sakurai and Hitoshi Ohta and Takashi Yamamoto and Yasuaki Einaga",
year = "2015",
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T1 - Novel Fe(II) spin crossover complexes involving a chalcogen-bond and π-stacking interactions with a paramagnetic and nonmagnetic M(dmit)2 anion (M = Ni, Au; Dmit = 4,5-dithiolato-1,3-dithiole-2-thione)

AU - Okai, Mitsunobu

AU - Takahashi, Kazuyuki

AU - Sakurai, Takahiro

AU - Ohta, Hitoshi

AU - Yamamoto, Takashi

AU - Einaga, Yasuaki

PY - 2015/8/14

Y1 - 2015/8/14

N2 - To introduce both an inter-sulphur atom and π-stacking interaction between a spin crossover (SCO) cation and paramagnetic anion, we designed and synthesised two novel Fe(ii) SCO compounds involving a terpyridine-type thiazole containing ligand with the paramagnetic Ni(dmit)2 and nonmagnetic Au(dmit)2 anion (dmit = 4,5-dithiolato-1,3-dithiole-2-thione). The temperature variations of magnetic susceptibility and Mössbauer spectroscopy revealed that both complexes exhibited an almost complete SCO conversion, and moreover, the Ni(dmit)2 anion was in a paramagnetic state down to 2 K. The crystal structures for the Ni(dmit)2 complex at 213 and 400 K indicated that the chalcogen-bond and π-stacking interaction would be enhanced by the electrostatic interaction between the cation and anion, preventing the π-radicals from dimerising. The light-induced excited spin state trapping effect was observed at 5 K.

AB - To introduce both an inter-sulphur atom and π-stacking interaction between a spin crossover (SCO) cation and paramagnetic anion, we designed and synthesised two novel Fe(ii) SCO compounds involving a terpyridine-type thiazole containing ligand with the paramagnetic Ni(dmit)2 and nonmagnetic Au(dmit)2 anion (dmit = 4,5-dithiolato-1,3-dithiole-2-thione). The temperature variations of magnetic susceptibility and Mössbauer spectroscopy revealed that both complexes exhibited an almost complete SCO conversion, and moreover, the Ni(dmit)2 anion was in a paramagnetic state down to 2 K. The crystal structures for the Ni(dmit)2 complex at 213 and 400 K indicated that the chalcogen-bond and π-stacking interaction would be enhanced by the electrostatic interaction between the cation and anion, preventing the π-radicals from dimerising. The light-induced excited spin state trapping effect was observed at 5 K.

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