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 language | English |
|---|---|
| Pages (from-to) | 1517-1523 |
| Number of pages | 7 |
| Journal | Inorganic Chemistry |
| Volume | 49 |
| Issue number | 4 |
| DOIs | |
| Publication status | Published - Feb 15 2010 |
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ASJC Scopus subject areas
- Inorganic Chemistry
- Physical and Theoretical Chemistry
Cite this
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 journal › Article
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TY - JOUR
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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UR - http://www.scopus.com/inward/citedby.url?scp=77249094602&partnerID=8YFLogxK
U2 - 10.1021/ic9017344
DO - 10.1021/ic9017344
M3 - Article
C2 - 20092285
AN - SCOPUS:77249094602
VL - 49
SP - 1517
EP - 1523
JO - Inorganic Chemistry
JF - Inorganic Chemistry
SN - 0020-1669
IS - 4
ER -