One-dimensional Spin-crossover iron(II) complexes bridged by intermolecular imidazole-pyridine NH· · · N hydrogen bonds, [Fe(HLMe)3]X2 (HLMe = (2-Methylimidazol-4-yl-methylideneamino-2-ethylpyridine; X = PF6, ClO4, BF4)

Koshiro Nishi, Shinobu Arata, Naohide Matsumoto, Seiichiro Iijima, Yukinari Sunatsuki, Hiroyuki Ishida, Masaaki Kojima

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Abstract

2-Methylimidazol-4-yl-methylideneamino-2-ethylpyridine (abbreviated as HLMe) is the 1:1 condensation product of 2-methyl-4-formylimidazole and 2-aminoethylpyridine and functions as a bidentate ligand to the iron(II) ion to produce the 3:1 complexes together with anions, [Fe(HLMe) 3]X2 (X = PF6 (1), ClO4 (2), BF 4 (3)). The magnetic susceptibilities, differential scanning calorimetric measurements, and M̈ossbauer spectral measurements demonstrated that complexes 1, 2, and 3 showed a steep one-step spin crossover (SCO) between the high-spin (HS, S=2) and low-spin (LS, S=0) states with small thermal hysteresis. Three complexes have an isomorphous structure and are crystallized in the same monoclinic space group, C2/c, both in the HS and LS states. The iron(II) ion has the octahedral coordination geometry of a facial isomer with N6 donor atoms of three bidentate ligands, in which an imidazole and an imine nitrogen atom per ligand participate in the formation of the coordination bond, but the pyridine nitrogen is free from coordination. The complex cation fac-[Fe(HLMe)3]2+ is a chiral species with a δ or δ isomer, and the adjacent δ and δ isomers are linked alternately by an intermolecular imidazole-pyridine NH· · · N hydrogen bond to produce an achiral 1D chain. The two remaining imidazole moieties per complex are hydrogen-bonded to the anions that occupy the space among the chains. The SCOprofile becomes steeper with the decrease of the anion size (73.0 Å 3 for PF6-, 54.4 Å 3 for ClO4-, and 53.4 Å 3 for BF4-). The SCO transition temperature T1/2 of the PF 6 (1), ClO4 (2), and BF4 (3) salts estimated from the magnetic susceptibility measurements are (T↓ = 151.8 K, T↑ = 155.3 K), (T =184.5K, T = 186.0 K), and (T = 146.4 K, T =148.2K), respectively, indicating that the T1/2 value is not in accord with the anion size.

Original languageEnglish
Pages (from-to)1517-1523
Number of pages7
JournalInorganic Chemistry
Volume49
Issue number4
DOIs
Publication statusPublished - Feb 15 2010

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imidazoles
Anions
pyridines
crossovers
Hydrogen bonds
Iron
Isomers
hydrogen bonds
anions
iron
isomers
Ligands
Magnetic susceptibility
ligands
Nitrogen
Ions
magnetic permeability
Atoms
Imines
nitrogen atoms

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry

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One-dimensional Spin-crossover iron(II) complexes bridged by intermolecular imidazole-pyridine NH· · · N hydrogen bonds, [Fe(HLMe)3]X2 (HLMe = (2-Methylimidazol-4-yl-methylideneamino-2-ethylpyridine; X = PF6, ClO4, BF4). / Nishi, Koshiro; Arata, Shinobu; Matsumoto, Naohide; Iijima, Seiichiro; Sunatsuki, Yukinari; Ishida, Hiroyuki; Kojima, Masaaki.

In: Inorganic Chemistry, Vol. 49, No. 4, 15.02.2010, p. 1517-1523.

Research output: Contribution to journalArticle

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title = "One-dimensional Spin-crossover iron(II) complexes bridged by intermolecular imidazole-pyridine NH· · · N hydrogen bonds, [Fe(HLMe)3]X2 (HLMe = (2-Methylimidazol-4-yl-methylideneamino-2-ethylpyridine; X = PF6, ClO4, BF4)",
abstract = "2-Methylimidazol-4-yl-methylideneamino-2-ethylpyridine (abbreviated as HLMe) is the 1:1 condensation product of 2-methyl-4-formylimidazole and 2-aminoethylpyridine and functions as a bidentate ligand to the iron(II) ion to produce the 3:1 complexes together with anions, [Fe(HLMe) 3]X2 (X = PF6 (1), ClO4 (2), BF 4 (3)). The magnetic susceptibilities, differential scanning calorimetric measurements, and M̈ossbauer spectral measurements demonstrated that complexes 1, 2, and 3 showed a steep one-step spin crossover (SCO) between the high-spin (HS, S=2) and low-spin (LS, S=0) states with small thermal hysteresis. Three complexes have an isomorphous structure and are crystallized in the same monoclinic space group, C2/c, both in the HS and LS states. The iron(II) ion has the octahedral coordination geometry of a facial isomer with N6 donor atoms of three bidentate ligands, in which an imidazole and an imine nitrogen atom per ligand participate in the formation of the coordination bond, but the pyridine nitrogen is free from coordination. The complex cation fac-[Fe(HLMe)3]2+ is a chiral species with a δ or δ isomer, and the adjacent δ and δ isomers are linked alternately by an intermolecular imidazole-pyridine NH· · · N hydrogen bond to produce an achiral 1D chain. The two remaining imidazole moieties per complex are hydrogen-bonded to the anions that occupy the space among the chains. The SCOprofile becomes steeper with the decrease of the anion size (73.0 {\AA} 3 for PF6-, 54.4 {\AA} 3 for ClO4-, and 53.4 {\AA} 3 for BF4-). The SCO transition temperature T1/2 of the PF 6 (1), ClO4 (2), and BF4 (3) salts estimated from the magnetic susceptibility measurements are (T↓ = 151.8 K, T↑ = 155.3 K), (T =184.5K, T = 186.0 K), and (T = 146.4 K, T =148.2K), respectively, indicating that the T1/2 value is not in accord with the anion size.",
author = "Koshiro Nishi and Shinobu Arata and Naohide Matsumoto and Seiichiro Iijima and Yukinari Sunatsuki and Hiroyuki Ishida and Masaaki Kojima",
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T1 - One-dimensional Spin-crossover iron(II) complexes bridged by intermolecular imidazole-pyridine NH· · · N hydrogen bonds, [Fe(HLMe)3]X2 (HLMe = (2-Methylimidazol-4-yl-methylideneamino-2-ethylpyridine; X = PF6, ClO4, BF4)

AU - Nishi, Koshiro

AU - Arata, Shinobu

AU - Matsumoto, Naohide

AU - Iijima, Seiichiro

AU - Sunatsuki, Yukinari

AU - Ishida, Hiroyuki

AU - Kojima, Masaaki

PY - 2010/2/15

Y1 - 2010/2/15

N2 - 2-Methylimidazol-4-yl-methylideneamino-2-ethylpyridine (abbreviated as HLMe) is the 1:1 condensation product of 2-methyl-4-formylimidazole and 2-aminoethylpyridine and functions as a bidentate ligand to the iron(II) ion to produce the 3:1 complexes together with anions, [Fe(HLMe) 3]X2 (X = PF6 (1), ClO4 (2), BF 4 (3)). The magnetic susceptibilities, differential scanning calorimetric measurements, and M̈ossbauer spectral measurements demonstrated that complexes 1, 2, and 3 showed a steep one-step spin crossover (SCO) between the high-spin (HS, S=2) and low-spin (LS, S=0) states with small thermal hysteresis. Three complexes have an isomorphous structure and are crystallized in the same monoclinic space group, C2/c, both in the HS and LS states. The iron(II) ion has the octahedral coordination geometry of a facial isomer with N6 donor atoms of three bidentate ligands, in which an imidazole and an imine nitrogen atom per ligand participate in the formation of the coordination bond, but the pyridine nitrogen is free from coordination. The complex cation fac-[Fe(HLMe)3]2+ is a chiral species with a δ or δ isomer, and the adjacent δ and δ isomers are linked alternately by an intermolecular imidazole-pyridine NH· · · N hydrogen bond to produce an achiral 1D chain. The two remaining imidazole moieties per complex are hydrogen-bonded to the anions that occupy the space among the chains. The SCOprofile becomes steeper with the decrease of the anion size (73.0 Å 3 for PF6-, 54.4 Å 3 for ClO4-, and 53.4 Å 3 for BF4-). The SCO transition temperature T1/2 of the PF 6 (1), ClO4 (2), and BF4 (3) salts estimated from the magnetic susceptibility measurements are (T↓ = 151.8 K, T↑ = 155.3 K), (T =184.5K, T = 186.0 K), and (T = 146.4 K, T =148.2K), respectively, indicating that the T1/2 value is not in accord with the anion size.

AB - 2-Methylimidazol-4-yl-methylideneamino-2-ethylpyridine (abbreviated as HLMe) is the 1:1 condensation product of 2-methyl-4-formylimidazole and 2-aminoethylpyridine and functions as a bidentate ligand to the iron(II) ion to produce the 3:1 complexes together with anions, [Fe(HLMe) 3]X2 (X = PF6 (1), ClO4 (2), BF 4 (3)). The magnetic susceptibilities, differential scanning calorimetric measurements, and M̈ossbauer spectral measurements demonstrated that complexes 1, 2, and 3 showed a steep one-step spin crossover (SCO) between the high-spin (HS, S=2) and low-spin (LS, S=0) states with small thermal hysteresis. Three complexes have an isomorphous structure and are crystallized in the same monoclinic space group, C2/c, both in the HS and LS states. The iron(II) ion has the octahedral coordination geometry of a facial isomer with N6 donor atoms of three bidentate ligands, in which an imidazole and an imine nitrogen atom per ligand participate in the formation of the coordination bond, but the pyridine nitrogen is free from coordination. The complex cation fac-[Fe(HLMe)3]2+ is a chiral species with a δ or δ isomer, and the adjacent δ and δ isomers are linked alternately by an intermolecular imidazole-pyridine NH· · · N hydrogen bond to produce an achiral 1D chain. The two remaining imidazole moieties per complex are hydrogen-bonded to the anions that occupy the space among the chains. The SCOprofile becomes steeper with the decrease of the anion size (73.0 Å 3 for PF6-, 54.4 Å 3 for ClO4-, and 53.4 Å 3 for BF4-). The SCO transition temperature T1/2 of the PF 6 (1), ClO4 (2), and BF4 (3) salts estimated from the magnetic susceptibility measurements are (T↓ = 151.8 K, T↑ = 155.3 K), (T =184.5K, T = 186.0 K), and (T = 146.4 K, T =148.2K), respectively, indicating that the T1/2 value is not in accord with the anion size.

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