Facial and meridional geometrical isomers of tris(2-methylimidazol-4-yl- methylideneaminobenzyl)iron(II) with Δ- And Λ-configurations and their enantio-discriminative assembly via imidazole⋯chloride hydrogen bonding and spin cross-over properties

Daisuke Furushou; Tomotaka Hashibe; Takeshi Fujinami; Koshiro Nishi; Hiroaki Hagiwara; Naohide Matsumoto; Yukinari Sunatsuki; Masaaki Kojima; Seiichiro Iijima

doi:10.1016/j.poly.2012.06.085

Facial and meridional geometrical isomers of tris(2-methylimidazol-4-yl- methylideneaminobenzyl)iron(II) with Δ- And Λ-configurations and their enantio-discriminative assembly via imidazole⋯chloride hydrogen bonding and spin cross-over properties

Daisuke Furushou, Tomotaka Hashibe, Takeshi Fujinami, Koshiro Nishi, Hiroaki Hagiwara, Naohide Matsumoto, Yukinari Sunatsuki, Masaaki Kojima, Seiichiro Iijima

Advanced Science Research Center

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12 Citations (Scopus)

Abstract

A bidentate 2-methylimidazol-4-yl-methylideneaminobenzyl ligand (HL ^Me-Benz) reacts with Fe ^IICl ₂·4H ₂O and NaPF ₆ at a 3:1:1 molar ratio to yield a tris(2-methylimidazol-4-yl-methylideneaminobenzyl)iron(II) chloride hexafluorophosphate solvate with the formula of [Fe ^II(HL ^Me-Benz) ₃]Cl·PF ₆·solvent. Meridional and facial geometrical isomers, i.e., mer-[Fe ^II (HL ^Me-Benz) ₃]Cl·PF ₆·1.5H ₂O (1·PF ₆·1.5H ₂O) and fac-[Fe ^II(HL ^Me-Benz) ₃]Cl·PF ₆·EtOH·H ₂O (2·PF ₆· EtOH·H ₂O), were selectively crystallized from methanol and ethanol solutions, respectively. fac-[Fe ^II(HL ^Me-Benz) ₃]Cl·SbF ₆·H ₂O (2·SbF ₆·H ₂O) and fac-[Fe ^II(HL ^Me-Benz) ₃]Cl·ClO ₄·EtOH· H ₂O (2·ClO ₄·EtOH·H ₂O) are synthesized in ethanol, using the corresponding anions. Each Fe ^II ion has an octahedral coordination geometry with N ₆ donor atoms from three bidentate ligands. All three imidazole groups in both the fac- and mer-[Fe ^II(HL ^Me-Benz) ₃] ²⁺ cations are hydrogen-bonded to neighboring three Cl ^- ions, and each Cl ^- ion is hydrogen-bonded to three imidazole groups of three neighboring complex cations; this results in the formation of hydrogen-bonded assembly structures. mer-Complex 1·PF ₆·1.5H ₂O forms a heterochiral two-dimensional (2D) network structure comprised of cyclic {mer-[Fe ^II(HL ^Me-Benz) ₃] ²⁺⋯Cl ^-} ₃ units with an ΔΔΛ or ΛΛΔ configuration; the PF ₆ ^- ions occupy the spaces between the 2D layers. All the fac-complexes have isomorphous cubane-like tetrameric structures, i.e., {fac-[Fe ^II(HL ^Me-Benz) ₃] ²⁺⋯ Cl ^-} ₄. The tetranuclear structure comprises four homo-chiral fac-Δ- or fac-Λ-[Fe ^II(HL ^Me-Benz) ₃] ²⁺ cations and four Cl ^- ions interconnected by twelve imidazole-chloride hydrogen bonds to form a chiral cubane supramolecule that encapsulates one counter anion. In the crystal lattice, the cubane-like tetramers with opposite chiralities are alternately arrayed. The temperature dependence of the magnetic susceptibilities and Mössbauer spectra reveal that the fac-complexes show incomplete spin crossover behavior, while the mer-complex shows a gradual spin crossover between high-spin (HS, S = 2) and low-spin (LS, S = 0) states.

Original language	English
Pages (from-to)	194-203
Number of pages	10
Journal	Polyhedron
Volume	44
Issue number	1
DOIs	https://doi.org/10.1016/j.poly.2012.06.085
Publication status	Published - Aug 31 2012

Keywords

Bidentate ligand
Geometrical isomer
Hydrogen bond
Iron(II) complex
Optical isomer
Spin crossover

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry
Materials Chemistry

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Furushou, D., Hashibe, T., Fujinami, T., Nishi, K., Hagiwara, H., Matsumoto, N., Sunatsuki, Y., Kojima, M., & Iijima, S. (2012). Facial and meridional geometrical isomers of tris(2-methylimidazol-4-yl- methylideneaminobenzyl)iron(II) with Δ- And Λ-configurations and their enantio-discriminative assembly via imidazole⋯chloride hydrogen bonding and spin cross-over properties. Polyhedron, 44(1), 194-203. https://doi.org/10.1016/j.poly.2012.06.085

Facial and meridional geometrical isomers of tris(2-methylimidazol-4-yl- methylideneaminobenzyl)iron(II) with Δ- And Λ-configurations and their enantio-discriminative assembly via imidazole⋯chloride hydrogen bonding and spin cross-over properties. / Furushou, Daisuke; Hashibe, Tomotaka; Fujinami, Takeshi et al.
In: Polyhedron, Vol. 44, No. 1, 31.08.2012, p. 194-203.

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

Furushou, D, Hashibe, T, Fujinami, T, Nishi, K, Hagiwara, H, Matsumoto, N, Sunatsuki, Y, Kojima, M & Iijima, S 2012, 'Facial and meridional geometrical isomers of tris(2-methylimidazol-4-yl- methylideneaminobenzyl)iron(II) with Δ- And Λ-configurations and their enantio-discriminative assembly via imidazole⋯chloride hydrogen bonding and spin cross-over properties', Polyhedron, vol. 44, no. 1, pp. 194-203. https://doi.org/10.1016/j.poly.2012.06.085

Furushou D, Hashibe T, Fujinami T, Nishi K, Hagiwara H, Matsumoto N et al. Facial and meridional geometrical isomers of tris(2-methylimidazol-4-yl- methylideneaminobenzyl)iron(II) with Δ- And Λ-configurations and their enantio-discriminative assembly via imidazole⋯chloride hydrogen bonding and spin cross-over properties. Polyhedron. 2012 Aug 31;44(1):194-203. doi: 10.1016/j.poly.2012.06.085

Furushou, Daisuke ; Hashibe, Tomotaka ; Fujinami, Takeshi et al. / Facial and meridional geometrical isomers of tris(2-methylimidazol-4-yl- methylideneaminobenzyl)iron(II) with Δ- And Λ-configurations and their enantio-discriminative assembly via imidazole⋯chloride hydrogen bonding and spin cross-over properties. In: Polyhedron. 2012 ; Vol. 44, No. 1. pp. 194-203.

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title = "Facial and meridional geometrical isomers of tris(2-methylimidazol-4-yl- methylideneaminobenzyl)iron(II) with Δ- And Λ-configurations and their enantio-discriminative assembly via imidazole⋯chloride hydrogen bonding and spin cross-over properties",

abstract = "A bidentate 2-methylimidazol-4-yl-methylideneaminobenzyl ligand (HL Me-Benz) reacts with Fe IICl 2·4H 2O and NaPF 6 at a 3:1:1 molar ratio to yield a tris(2-methylimidazol-4-yl-methylideneaminobenzyl)iron(II) chloride hexafluorophosphate solvate with the formula of [Fe II(HL Me-Benz) 3]Cl·PF 6·solvent. Meridional and facial geometrical isomers, i.e., mer-[Fe II (HL Me-Benz) 3]Cl·PF 6·1.5H 2O (1·PF 6·1.5H 2O) and fac-[Fe II(HL Me-Benz) 3]Cl·PF 6·EtOH·H 2O (2·PF 6· EtOH·H 2O), were selectively crystallized from methanol and ethanol solutions, respectively. fac-[Fe II(HL Me-Benz) 3]Cl·SbF 6·H 2O (2·SbF 6·H 2O) and fac-[Fe II(HL Me-Benz) 3]Cl·ClO 4·EtOH· H 2O (2·ClO 4·EtOH·H 2O) are synthesized in ethanol, using the corresponding anions. Each Fe II ion has an octahedral coordination geometry with N 6 donor atoms from three bidentate ligands. All three imidazole groups in both the fac- and mer-[Fe II(HL Me-Benz) 3] 2+ cations are hydrogen-bonded to neighboring three Cl - ions, and each Cl - ion is hydrogen-bonded to three imidazole groups of three neighboring complex cations; this results in the formation of hydrogen-bonded assembly structures. mer-Complex 1·PF 6·1.5H 2O forms a heterochiral two-dimensional (2D) network structure comprised of cyclic {mer-[Fe II(HL Me-Benz) 3] 2+⋯Cl -} 3 units with an ΔΔΛ or ΛΛΔ configuration; the PF 6 - ions occupy the spaces between the 2D layers. All the fac-complexes have isomorphous cubane-like tetrameric structures, i.e., {fac-[Fe II(HL Me-Benz) 3] 2+⋯ Cl -} 4. The tetranuclear structure comprises four homo-chiral fac-Δ- or fac-Λ-[Fe II(HL Me-Benz) 3] 2+ cations and four Cl - ions interconnected by twelve imidazole-chloride hydrogen bonds to form a chiral cubane supramolecule that encapsulates one counter anion. In the crystal lattice, the cubane-like tetramers with opposite chiralities are alternately arrayed. The temperature dependence of the magnetic susceptibilities and M{\"o}ssbauer spectra reveal that the fac-complexes show incomplete spin crossover behavior, while the mer-complex shows a gradual spin crossover between high-spin (HS, S = 2) and low-spin (LS, S = 0) states.",

keywords = "Bidentate ligand, Geometrical isomer, Hydrogen bond, Iron(II) complex, Optical isomer, Spin crossover",

author = "Daisuke Furushou and Tomotaka Hashibe and Takeshi Fujinami and Koshiro Nishi and Hiroaki Hagiwara and Naohide Matsumoto and Yukinari Sunatsuki and Masaaki Kojima and Seiichiro Iijima",

note = "Funding Information: T. Hashibe, K. Nishi, T. Fujinami, and H. Hagiwara were supported by the Research Fellowship for young scientists of the Japan Society for the Promotion of Science . Copyright: Copyright 2012 Elsevier B.V., All rights reserved.",

year = "2012",

month = aug,

day = "31",

doi = "10.1016/j.poly.2012.06.085",

language = "English",

volume = "44",

pages = "194--203",

journal = "Polyhedron",

issn = "0277-5387",

publisher = "Elsevier Limited",

number = "1",

}

TY - JOUR

T1 - Facial and meridional geometrical isomers of tris(2-methylimidazol-4-yl- methylideneaminobenzyl)iron(II) with Δ- And Λ-configurations and their enantio-discriminative assembly via imidazole⋯chloride hydrogen bonding and spin cross-over properties

AU - Furushou, Daisuke

AU - Hashibe, Tomotaka

AU - Fujinami, Takeshi

AU - Nishi, Koshiro

AU - Hagiwara, Hiroaki

AU - Matsumoto, Naohide

AU - Sunatsuki, Yukinari

AU - Kojima, Masaaki

AU - Iijima, Seiichiro

N1 - Funding Information: T. Hashibe, K. Nishi, T. Fujinami, and H. Hagiwara were supported by the Research Fellowship for young scientists of the Japan Society for the Promotion of Science . Copyright: Copyright 2012 Elsevier B.V., All rights reserved.

PY - 2012/8/31

Y1 - 2012/8/31

N2 - A bidentate 2-methylimidazol-4-yl-methylideneaminobenzyl ligand (HL Me-Benz) reacts with Fe IICl 2·4H 2O and NaPF 6 at a 3:1:1 molar ratio to yield a tris(2-methylimidazol-4-yl-methylideneaminobenzyl)iron(II) chloride hexafluorophosphate solvate with the formula of [Fe II(HL Me-Benz) 3]Cl·PF 6·solvent. Meridional and facial geometrical isomers, i.e., mer-[Fe II (HL Me-Benz) 3]Cl·PF 6·1.5H 2O (1·PF 6·1.5H 2O) and fac-[Fe II(HL Me-Benz) 3]Cl·PF 6·EtOH·H 2O (2·PF 6· EtOH·H 2O), were selectively crystallized from methanol and ethanol solutions, respectively. fac-[Fe II(HL Me-Benz) 3]Cl·SbF 6·H 2O (2·SbF 6·H 2O) and fac-[Fe II(HL Me-Benz) 3]Cl·ClO 4·EtOH· H 2O (2·ClO 4·EtOH·H 2O) are synthesized in ethanol, using the corresponding anions. Each Fe II ion has an octahedral coordination geometry with N 6 donor atoms from three bidentate ligands. All three imidazole groups in both the fac- and mer-[Fe II(HL Me-Benz) 3] 2+ cations are hydrogen-bonded to neighboring three Cl - ions, and each Cl - ion is hydrogen-bonded to three imidazole groups of three neighboring complex cations; this results in the formation of hydrogen-bonded assembly structures. mer-Complex 1·PF 6·1.5H 2O forms a heterochiral two-dimensional (2D) network structure comprised of cyclic {mer-[Fe II(HL Me-Benz) 3] 2+⋯Cl -} 3 units with an ΔΔΛ or ΛΛΔ configuration; the PF 6 - ions occupy the spaces between the 2D layers. All the fac-complexes have isomorphous cubane-like tetrameric structures, i.e., {fac-[Fe II(HL Me-Benz) 3] 2+⋯ Cl -} 4. The tetranuclear structure comprises four homo-chiral fac-Δ- or fac-Λ-[Fe II(HL Me-Benz) 3] 2+ cations and four Cl - ions interconnected by twelve imidazole-chloride hydrogen bonds to form a chiral cubane supramolecule that encapsulates one counter anion. In the crystal lattice, the cubane-like tetramers with opposite chiralities are alternately arrayed. The temperature dependence of the magnetic susceptibilities and Mössbauer spectra reveal that the fac-complexes show incomplete spin crossover behavior, while the mer-complex shows a gradual spin crossover between high-spin (HS, S = 2) and low-spin (LS, S = 0) states.

AB - A bidentate 2-methylimidazol-4-yl-methylideneaminobenzyl ligand (HL Me-Benz) reacts with Fe IICl 2·4H 2O and NaPF 6 at a 3:1:1 molar ratio to yield a tris(2-methylimidazol-4-yl-methylideneaminobenzyl)iron(II) chloride hexafluorophosphate solvate with the formula of [Fe II(HL Me-Benz) 3]Cl·PF 6·solvent. Meridional and facial geometrical isomers, i.e., mer-[Fe II (HL Me-Benz) 3]Cl·PF 6·1.5H 2O (1·PF 6·1.5H 2O) and fac-[Fe II(HL Me-Benz) 3]Cl·PF 6·EtOH·H 2O (2·PF 6· EtOH·H 2O), were selectively crystallized from methanol and ethanol solutions, respectively. fac-[Fe II(HL Me-Benz) 3]Cl·SbF 6·H 2O (2·SbF 6·H 2O) and fac-[Fe II(HL Me-Benz) 3]Cl·ClO 4·EtOH· H 2O (2·ClO 4·EtOH·H 2O) are synthesized in ethanol, using the corresponding anions. Each Fe II ion has an octahedral coordination geometry with N 6 donor atoms from three bidentate ligands. All three imidazole groups in both the fac- and mer-[Fe II(HL Me-Benz) 3] 2+ cations are hydrogen-bonded to neighboring three Cl - ions, and each Cl - ion is hydrogen-bonded to three imidazole groups of three neighboring complex cations; this results in the formation of hydrogen-bonded assembly structures. mer-Complex 1·PF 6·1.5H 2O forms a heterochiral two-dimensional (2D) network structure comprised of cyclic {mer-[Fe II(HL Me-Benz) 3] 2+⋯Cl -} 3 units with an ΔΔΛ or ΛΛΔ configuration; the PF 6 - ions occupy the spaces between the 2D layers. All the fac-complexes have isomorphous cubane-like tetrameric structures, i.e., {fac-[Fe II(HL Me-Benz) 3] 2+⋯ Cl -} 4. The tetranuclear structure comprises four homo-chiral fac-Δ- or fac-Λ-[Fe II(HL Me-Benz) 3] 2+ cations and four Cl - ions interconnected by twelve imidazole-chloride hydrogen bonds to form a chiral cubane supramolecule that encapsulates one counter anion. In the crystal lattice, the cubane-like tetramers with opposite chiralities are alternately arrayed. The temperature dependence of the magnetic susceptibilities and Mössbauer spectra reveal that the fac-complexes show incomplete spin crossover behavior, while the mer-complex shows a gradual spin crossover between high-spin (HS, S = 2) and low-spin (LS, S = 0) states.

KW - Bidentate ligand

KW - Geometrical isomer

KW - Hydrogen bond

KW - Iron(II) complex

KW - Optical isomer

KW - Spin crossover

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Facial and meridional geometrical isomers of tris(2-methylimidazol-4-yl- methylideneaminobenzyl)iron(II) with Δ- And Λ-configurations and their enantio-discriminative assembly via imidazole⋯chloride hydrogen bonding and spin cross-over properties

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