Reprint of "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.2013.02.003

Reprint of "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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6 Citations (Scopus)

Abstract

A bidentate 2-methylimidazol-4-yl-methylideneaminobenzyl ligand (HL ^Me-Benz) reacts with Fe^IICl₂·4H ₂O and NaPF₆ 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·PF₆·solvent. Meridional and facial geometrical isomers, i.e., mer-[Fe^II (HL ^Me-Benz)₃]Cl·PF₆·1.5H ₂O (1·PF₆·1.5H₂O) and fac-[Fe^II(HL^Me-Benz)₃]Cl·PF ₆·EtOH·H₂O (2·PF₆· EtOH·H₂O), were selectively crystallized from methanol and ethanol solutions, respectively. fac-[Fe^II(HL^Me-Benz) ₃]Cl·SbF₆·H₂O (2·SbF ₆·H₂O) and fac-[Fe^II(HL ^Me-Benz)₃]Cl·ClO₄·EtOH· H₂O (2·ClO₄·EtOH·H₂O) are synthesized in ethanol, using the corresponding anions. Each Fe^II ion has an octahedral coordination geometry with N₆ 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·PF₆·1.5H 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)	1489-1498
Number of pages	10
Journal	Polyhedron
Volume	52
DOIs	https://doi.org/10.1016/j.poly.2013.02.003
Publication status	Published - Mar 22 2013

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. (2013). Reprint of "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, 52, 1489-1498. https://doi.org/10.1016/j.poly.2013.02.003

Reprint of "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. 52, 22.03.2013, p. 1489-1498.

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 2013, 'Reprint of "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. 52, pp. 1489-1498. https://doi.org/10.1016/j.poly.2013.02.003

Furushou D, Hashibe T, Fujinami T, Nishi K, Hagiwara H, Matsumoto N et al. Reprint of "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. 2013 Mar 22;52:1489-1498. doi: 10.1016/j.poly.2013.02.003

Furushou, Daisuke ; Hashibe, Tomotaka ; Fujinami, Takeshi et al. / Reprint of "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. 2013 ; Vol. 52. pp. 1489-1498.

@article{7479153800cf4e2da0b0c37f9b12b56c,

title = "Reprint of {"}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 FeIICl2·4H 2O and NaPF6 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 [FeII(HL Me-Benz)3]Cl·PF6·solvent. Meridional and facial geometrical isomers, i.e., mer-[FeII (HL Me-Benz)3]Cl·PF6·1.5H 2O (1·PF6·1.5H2O) and fac-[FeII(HLMe-Benz)3]Cl·PF 6·EtOH·H2O (2·PF6· EtOH·H2O), were selectively crystallized from methanol and ethanol solutions, respectively. fac-[FeII(HLMe-Benz) 3]Cl·SbF6·H2O (2·SbF 6·H2O) and fac-[FeII(HL Me-Benz)3]Cl·ClO4·EtOH· H2O (2·ClO4·EtOH·H2O) are synthesized in ethanol, using the corresponding anions. Each FeII ion has an octahedral coordination geometry with N6 donor atoms from three bidentate ligands. All three imidazole groups in both the fac- and mer-[FeII(HLMe-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·PF6·1.5H 2O forms a heterochiral two-dimensional (2D) network structure comprised of cyclic {mer-[FeII(HLMe-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-[FeII(HLMe-Benz)3]2+⋯ Cl-}4. The tetranuclear structure comprises four homo-chiral fac-Δ- or fac-Λ-[FeII(HLMe-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 . ",

year = "2013",

month = mar,

day = "22",

doi = "10.1016/j.poly.2013.02.003",

language = "English",

volume = "52",

pages = "1489--1498",

journal = "Polyhedron",

issn = "0277-5387",

publisher = "Elsevier Limited",

}

TY - JOUR

T1 - Reprint of "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 .

PY - 2013/3/22

Y1 - 2013/3/22

N2 - A bidentate 2-methylimidazol-4-yl-methylideneaminobenzyl ligand (HL Me-Benz) reacts with FeIICl2·4H 2O and NaPF6 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 [FeII(HL Me-Benz)3]Cl·PF6·solvent. Meridional and facial geometrical isomers, i.e., mer-[FeII (HL Me-Benz)3]Cl·PF6·1.5H 2O (1·PF6·1.5H2O) and fac-[FeII(HLMe-Benz)3]Cl·PF 6·EtOH·H2O (2·PF6· EtOH·H2O), were selectively crystallized from methanol and ethanol solutions, respectively. fac-[FeII(HLMe-Benz) 3]Cl·SbF6·H2O (2·SbF 6·H2O) and fac-[FeII(HL Me-Benz)3]Cl·ClO4·EtOH· H2O (2·ClO4·EtOH·H2O) are synthesized in ethanol, using the corresponding anions. Each FeII ion has an octahedral coordination geometry with N6 donor atoms from three bidentate ligands. All three imidazole groups in both the fac- and mer-[FeII(HLMe-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·PF6·1.5H 2O forms a heterochiral two-dimensional (2D) network structure comprised of cyclic {mer-[FeII(HLMe-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-[FeII(HLMe-Benz)3]2+⋯ Cl-}4. The tetranuclear structure comprises four homo-chiral fac-Δ- or fac-Λ-[FeII(HLMe-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 FeIICl2·4H 2O and NaPF6 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 [FeII(HL Me-Benz)3]Cl·PF6·solvent. Meridional and facial geometrical isomers, i.e., mer-[FeII (HL Me-Benz)3]Cl·PF6·1.5H 2O (1·PF6·1.5H2O) and fac-[FeII(HLMe-Benz)3]Cl·PF 6·EtOH·H2O (2·PF6· EtOH·H2O), were selectively crystallized from methanol and ethanol solutions, respectively. fac-[FeII(HLMe-Benz) 3]Cl·SbF6·H2O (2·SbF 6·H2O) and fac-[FeII(HL Me-Benz)3]Cl·ClO4·EtOH· H2O (2·ClO4·EtOH·H2O) are synthesized in ethanol, using the corresponding anions. Each FeII ion has an octahedral coordination geometry with N6 donor atoms from three bidentate ligands. All three imidazole groups in both the fac- and mer-[FeII(HLMe-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·PF6·1.5H 2O forms a heterochiral two-dimensional (2D) network structure comprised of cyclic {mer-[FeII(HLMe-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-[FeII(HLMe-Benz)3]2+⋯ Cl-}4. The tetranuclear structure comprises four homo-chiral fac-Δ- or fac-Λ-[FeII(HLMe-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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U2 - 10.1016/j.poly.2013.02.003

DO - 10.1016/j.poly.2013.02.003

M3 - Article

AN - SCOPUS:84875450491

SN - 0277-5387

VL - 52

SP - 1489

EP - 1498

JO - Polyhedron

JF - Polyhedron

ER -

Reprint of "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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