1D and 2D assembly structures by imidazole⋯chloride hydrogen bonds of iron(ii) complexes [FeII(HLn-Pr)3] Cl·Y (HLn-Pr = 2-methylimidazol-4-yl-methylideneamino-n- propyl; Y = AsF6, BF4) and their spin states

Takeshi Fujinami, Koshiro Nishi, Naohide Matsumoto, Seiichiro Iijima, Malcolm A. Halcrow, Yukinari Sunatsuki, Masaaki Kojima

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Abstract

Two FeII complexes fac-[FeII(HLn-Pr) 3]Cl·Y (Y = AsF6 (1) and BF4 (2)) were synthesized, where HLn-Pr is 2-methylimidazole-4-yl-methylideneamino- n-propyl. Each complex-cation has the same octahedral N6 geometry coordinated by three bidentate ligands and assumes facial-isomerism, fac-[FeII(HLn-Pr)3]2+ with Δ- and Λ-enantiomorphs. Three imidazole groups per Δ- or Λ-fac-[FeII(HLn-Pr)3]2+ are hydrogen-bonded to three Cl- ions or, from the viewpoint of the Cl- ion, one Cl- ion is hydrogen-bonded to three neighbouring fac-[FeII(HLn-Pr)3]2+ cations. The 3:3 NH⋯Cl- hydrogen bonds between Δ- or Λ-fac-[FeII(HLn-Pr)3]2+ and Cl- generate two kinds of assembly structures. The directions of the 3:3 NH⋯Cl- hydrogen bonds and hence the resulting assembly structures are determined by the size of the anion Y, though Y is not involved into the network structure and just accommodated in the cavity. Compound 1 has a 1D ladder structure giving a larger cavity, in which the Δ- and Λ-fac-[FeII(HLn-Pr)3]2+ enantiomorphs are bridged by two NH⋯Cl- hydrogen bonds. Compound 2 has a 2D network structure with a net unit of a cyclic trimer of {fac-[FeII(HLn-Pr)3]2+⋯ Cl-}3 giving a smaller cavity, in which Δ- or Λ-fac-[FeII(HLn-Pr)3]2+ species with the same chirality are linked by NH⋯Cl- hydrogen bonds to give a homochiral 2D network structure. Magnetic susceptibility and Mössbauer spectral measurements demonstrated that compound 1 showed an abrupt one-step spin crossover with 4.0 K thermal hysteresis of T c↓ = 125.5 K and Tc↑ = 129.5 K and compound 2 showed no spin transition and stayed in the high-spin state over the 5-300 K temperature range.

Original languageEnglish
Pages (from-to)12301-12309
Number of pages9
JournalDalton Transactions
Volume40
Issue number45
DOIs
Publication statusPublished - Dec 7 2011

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Hydrogen bonds
Iron
Ions
Cations
Hydrogen
Chirality
Ladders
Magnetic susceptibility
Anions
Hysteresis
Ligands
Geometry
2-methylimidazole
Temperature

ASJC Scopus subject areas

  • Inorganic Chemistry

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1D and 2D assembly structures by imidazole⋯chloride hydrogen bonds of iron(ii) complexes [FeII(HLn-Pr)3] Cl·Y (HLn-Pr = 2-methylimidazol-4-yl-methylideneamino-n- propyl; Y = AsF6, BF4) and their spin states. / Fujinami, Takeshi; Nishi, Koshiro; Matsumoto, Naohide; Iijima, Seiichiro; Halcrow, Malcolm A.; Sunatsuki, Yukinari; Kojima, Masaaki.

In: Dalton Transactions, Vol. 40, No. 45, 07.12.2011, p. 12301-12309.

Research output: Contribution to journalArticle

Fujinami, Takeshi ; Nishi, Koshiro ; Matsumoto, Naohide ; Iijima, Seiichiro ; Halcrow, Malcolm A. ; Sunatsuki, Yukinari ; Kojima, Masaaki. / 1D and 2D assembly structures by imidazole⋯chloride hydrogen bonds of iron(ii) complexes [FeII(HLn-Pr)3] Cl·Y (HLn-Pr = 2-methylimidazol-4-yl-methylideneamino-n- propyl; Y = AsF6, BF4) and their spin states. In: Dalton Transactions. 2011 ; Vol. 40, No. 45. pp. 12301-12309.
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abstract = "Two FeII complexes fac-[FeII(HLn-Pr) 3]Cl·Y (Y = AsF6 (1) and BF4 (2)) were synthesized, where HLn-Pr is 2-methylimidazole-4-yl-methylideneamino- n-propyl. Each complex-cation has the same octahedral N6 geometry coordinated by three bidentate ligands and assumes facial-isomerism, fac-[FeII(HLn-Pr)3]2+ with Δ- and Λ-enantiomorphs. Three imidazole groups per Δ- or Λ-fac-[FeII(HLn-Pr)3]2+ are hydrogen-bonded to three Cl- ions or, from the viewpoint of the Cl- ion, one Cl- ion is hydrogen-bonded to three neighbouring fac-[FeII(HLn-Pr)3]2+ cations. The 3:3 NH⋯Cl- hydrogen bonds between Δ- or Λ-fac-[FeII(HLn-Pr)3]2+ and Cl- generate two kinds of assembly structures. The directions of the 3:3 NH⋯Cl- hydrogen bonds and hence the resulting assembly structures are determined by the size of the anion Y, though Y is not involved into the network structure and just accommodated in the cavity. Compound 1 has a 1D ladder structure giving a larger cavity, in which the Δ- and Λ-fac-[FeII(HLn-Pr)3]2+ enantiomorphs are bridged by two NH⋯Cl- hydrogen bonds. Compound 2 has a 2D network structure with a net unit of a cyclic trimer of {fac-[FeII(HLn-Pr)3]2+⋯ Cl-}3 giving a smaller cavity, in which Δ- or Λ-fac-[FeII(HLn-Pr)3]2+ species with the same chirality are linked by NH⋯Cl- hydrogen bonds to give a homochiral 2D network structure. Magnetic susceptibility and M{\"o}ssbauer spectral measurements demonstrated that compound 1 showed an abrupt one-step spin crossover with 4.0 K thermal hysteresis of T c↓ = 125.5 K and Tc↑ = 129.5 K and compound 2 showed no spin transition and stayed in the high-spin state over the 5-300 K temperature range.",
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T1 - 1D and 2D assembly structures by imidazole⋯chloride hydrogen bonds of iron(ii) complexes [FeII(HLn-Pr)3] Cl·Y (HLn-Pr = 2-methylimidazol-4-yl-methylideneamino-n- propyl; Y = AsF6, BF4) and their spin states

AU - Fujinami, Takeshi

AU - Nishi, Koshiro

AU - Matsumoto, Naohide

AU - Iijima, Seiichiro

AU - Halcrow, Malcolm A.

AU - Sunatsuki, Yukinari

AU - Kojima, Masaaki

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N2 - Two FeII complexes fac-[FeII(HLn-Pr) 3]Cl·Y (Y = AsF6 (1) and BF4 (2)) were synthesized, where HLn-Pr is 2-methylimidazole-4-yl-methylideneamino- n-propyl. Each complex-cation has the same octahedral N6 geometry coordinated by three bidentate ligands and assumes facial-isomerism, fac-[FeII(HLn-Pr)3]2+ with Δ- and Λ-enantiomorphs. Three imidazole groups per Δ- or Λ-fac-[FeII(HLn-Pr)3]2+ are hydrogen-bonded to three Cl- ions or, from the viewpoint of the Cl- ion, one Cl- ion is hydrogen-bonded to three neighbouring fac-[FeII(HLn-Pr)3]2+ cations. The 3:3 NH⋯Cl- hydrogen bonds between Δ- or Λ-fac-[FeII(HLn-Pr)3]2+ and Cl- generate two kinds of assembly structures. The directions of the 3:3 NH⋯Cl- hydrogen bonds and hence the resulting assembly structures are determined by the size of the anion Y, though Y is not involved into the network structure and just accommodated in the cavity. Compound 1 has a 1D ladder structure giving a larger cavity, in which the Δ- and Λ-fac-[FeII(HLn-Pr)3]2+ enantiomorphs are bridged by two NH⋯Cl- hydrogen bonds. Compound 2 has a 2D network structure with a net unit of a cyclic trimer of {fac-[FeII(HLn-Pr)3]2+⋯ Cl-}3 giving a smaller cavity, in which Δ- or Λ-fac-[FeII(HLn-Pr)3]2+ species with the same chirality are linked by NH⋯Cl- hydrogen bonds to give a homochiral 2D network structure. Magnetic susceptibility and Mössbauer spectral measurements demonstrated that compound 1 showed an abrupt one-step spin crossover with 4.0 K thermal hysteresis of T c↓ = 125.5 K and Tc↑ = 129.5 K and compound 2 showed no spin transition and stayed in the high-spin state over the 5-300 K temperature range.

AB - Two FeII complexes fac-[FeII(HLn-Pr) 3]Cl·Y (Y = AsF6 (1) and BF4 (2)) were synthesized, where HLn-Pr is 2-methylimidazole-4-yl-methylideneamino- n-propyl. Each complex-cation has the same octahedral N6 geometry coordinated by three bidentate ligands and assumes facial-isomerism, fac-[FeII(HLn-Pr)3]2+ with Δ- and Λ-enantiomorphs. Three imidazole groups per Δ- or Λ-fac-[FeII(HLn-Pr)3]2+ are hydrogen-bonded to three Cl- ions or, from the viewpoint of the Cl- ion, one Cl- ion is hydrogen-bonded to three neighbouring fac-[FeII(HLn-Pr)3]2+ cations. The 3:3 NH⋯Cl- hydrogen bonds between Δ- or Λ-fac-[FeII(HLn-Pr)3]2+ and Cl- generate two kinds of assembly structures. The directions of the 3:3 NH⋯Cl- hydrogen bonds and hence the resulting assembly structures are determined by the size of the anion Y, though Y is not involved into the network structure and just accommodated in the cavity. Compound 1 has a 1D ladder structure giving a larger cavity, in which the Δ- and Λ-fac-[FeII(HLn-Pr)3]2+ enantiomorphs are bridged by two NH⋯Cl- hydrogen bonds. Compound 2 has a 2D network structure with a net unit of a cyclic trimer of {fac-[FeII(HLn-Pr)3]2+⋯ Cl-}3 giving a smaller cavity, in which Δ- or Λ-fac-[FeII(HLn-Pr)3]2+ species with the same chirality are linked by NH⋯Cl- hydrogen bonds to give a homochiral 2D network structure. Magnetic susceptibility and Mössbauer spectral measurements demonstrated that compound 1 showed an abrupt one-step spin crossover with 4.0 K thermal hysteresis of T c↓ = 125.5 K and Tc↑ = 129.5 K and compound 2 showed no spin transition and stayed in the high-spin state over the 5-300 K temperature range.

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