Supramolecular spin-crossover iron complexes based on imidazole-imidazolate hydrogen bonds

Yukinari Sunatsuki, Hiromi Ohta, Masaaki Kojima, Yuichi Ikuta, Yoshiyuki Goto, Naohide Matsumoto, Seiichiro Iijima, Haruo Akashi, Sumio Kaizaki, Françoise Dahan, Jean Pierre Tuchagues

Research output: Contribution to journalArticle

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Abstract

The [FeII(H3L)](BF4)2· 3H2O (1) complex was synthesized, where H3L (tris{[2-{(imidazole-4-yl)methylidene}amino]ethyl}amine) is a tripodal ligand obtained by condensation of tris(2-aminoethyl)amine and 4-formylimidazole (fim) in a 1:3 molar ratio. Starting from 1, a series of complexes, [Fe II(H1.5L)](BF4)0.5 (2) (=[Fe II(H3L)][FeII(L)]BF4), [Fe-(H 1.5L)]BF4 (3) (=[FeII(H3L)][Fe III(L)](BF4)2), [FeIII(H 3L)](BF4)3·fim·H2O (4), and [FeIII(L)]·2.5H2O (5), has been synthesized and characterized. The single-crystal X-ray structure of each complex has been determined. The FeII compound, 2, and a mixed valence FeII-FeIII compound, 3, involve formally hemi-deprotonated ligands, H1.5L. The structure of 3 consists of a homochiral two-dimensional assembled sheet, arising from the intermolecular hydrogen bonds between [FeII(H3L)]2+ and [FeIII(L)]0 (3). All but 5 exhibit spin crossover between low-spin (LS) and high-spin (HS) states. This is a rare case where both Fe II and FeIII complexes containing the same ligand exhibit spin-crossover behavior. Magnetic susceptibility and Mössbauer studies showed that 3 has three accessible electronic states: LS FeII-LS FeIII, HS FeII-LS FeIII, and HS Fe II-HS FeIII. Compounds 1-3 show the light-induced excited spin-state trapping effect at the FeII sites upon irradiation with green light. The solution magnetic properties, electronic spectra, and electrochemical properties of 1, 4, and 5 were also studied.

Original languageEnglish
Pages (from-to)4154-4171
Number of pages18
JournalInorganic Chemistry
Volume43
Issue number14
Publication statusPublished - Jul 12 2004

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imidazoles
crossovers
Hydrogen bonds
Iron
hydrogen bonds
Ligands
iron
Methyl Green
Electronic states
Magnetic susceptibility
Electrochemical properties
Amines
Condensation
Magnetic properties
Irradiation
Single crystals
X rays
ligands
amines
imidazole

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Sunatsuki, Y., Ohta, H., Kojima, M., Ikuta, Y., Goto, Y., Matsumoto, N., ... Tuchagues, J. P. (2004). Supramolecular spin-crossover iron complexes based on imidazole-imidazolate hydrogen bonds. Inorganic Chemistry, 43(14), 4154-4171.

Supramolecular spin-crossover iron complexes based on imidazole-imidazolate hydrogen bonds. / Sunatsuki, Yukinari; Ohta, Hiromi; Kojima, Masaaki; Ikuta, Yuichi; Goto, Yoshiyuki; Matsumoto, Naohide; Iijima, Seiichiro; Akashi, Haruo; Kaizaki, Sumio; Dahan, Françoise; Tuchagues, Jean Pierre.

In: Inorganic Chemistry, Vol. 43, No. 14, 12.07.2004, p. 4154-4171.

Research output: Contribution to journalArticle

Sunatsuki, Y, Ohta, H, Kojima, M, Ikuta, Y, Goto, Y, Matsumoto, N, Iijima, S, Akashi, H, Kaizaki, S, Dahan, F & Tuchagues, JP 2004, 'Supramolecular spin-crossover iron complexes based on imidazole-imidazolate hydrogen bonds', Inorganic Chemistry, vol. 43, no. 14, pp. 4154-4171.
Sunatsuki Y, Ohta H, Kojima M, Ikuta Y, Goto Y, Matsumoto N et al. Supramolecular spin-crossover iron complexes based on imidazole-imidazolate hydrogen bonds. Inorganic Chemistry. 2004 Jul 12;43(14):4154-4171.
Sunatsuki, Yukinari ; Ohta, Hiromi ; Kojima, Masaaki ; Ikuta, Yuichi ; Goto, Yoshiyuki ; Matsumoto, Naohide ; Iijima, Seiichiro ; Akashi, Haruo ; Kaizaki, Sumio ; Dahan, Françoise ; Tuchagues, Jean Pierre. / Supramolecular spin-crossover iron complexes based on imidazole-imidazolate hydrogen bonds. In: Inorganic Chemistry. 2004 ; Vol. 43, No. 14. pp. 4154-4171.
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abstract = "The [FeII(H3L)](BF4)2· 3H2O (1) complex was synthesized, where H3L (tris{[2-{(imidazole-4-yl)methylidene}amino]ethyl}amine) is a tripodal ligand obtained by condensation of tris(2-aminoethyl)amine and 4-formylimidazole (fim) in a 1:3 molar ratio. Starting from 1, a series of complexes, [Fe II(H1.5L)](BF4)0.5 (2) (=[Fe II(H3L)][FeII(L)]BF4), [Fe-(H 1.5L)]BF4 (3) (=[FeII(H3L)][Fe III(L)](BF4)2), [FeIII(H 3L)](BF4)3·fim·H2O (4), and [FeIII(L)]·2.5H2O (5), has been synthesized and characterized. The single-crystal X-ray structure of each complex has been determined. The FeII compound, 2, and a mixed valence FeII-FeIII compound, 3, involve formally hemi-deprotonated ligands, H1.5L. The structure of 3 consists of a homochiral two-dimensional assembled sheet, arising from the intermolecular hydrogen bonds between [FeII(H3L)]2+ and [FeIII(L)]0 (3). All but 5 exhibit spin crossover between low-spin (LS) and high-spin (HS) states. This is a rare case where both Fe II and FeIII complexes containing the same ligand exhibit spin-crossover behavior. Magnetic susceptibility and M{\"o}ssbauer studies showed that 3 has three accessible electronic states: LS FeII-LS FeIII, HS FeII-LS FeIII, and HS Fe II-HS FeIII. Compounds 1-3 show the light-induced excited spin-state trapping effect at the FeII sites upon irradiation with green light. The solution magnetic properties, electronic spectra, and electrochemical properties of 1, 4, and 5 were also studied.",
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AU - Goto, Yoshiyuki

AU - Matsumoto, Naohide

AU - Iijima, Seiichiro

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N2 - The [FeII(H3L)](BF4)2· 3H2O (1) complex was synthesized, where H3L (tris{[2-{(imidazole-4-yl)methylidene}amino]ethyl}amine) is a tripodal ligand obtained by condensation of tris(2-aminoethyl)amine and 4-formylimidazole (fim) in a 1:3 molar ratio. Starting from 1, a series of complexes, [Fe II(H1.5L)](BF4)0.5 (2) (=[Fe II(H3L)][FeII(L)]BF4), [Fe-(H 1.5L)]BF4 (3) (=[FeII(H3L)][Fe III(L)](BF4)2), [FeIII(H 3L)](BF4)3·fim·H2O (4), and [FeIII(L)]·2.5H2O (5), has been synthesized and characterized. The single-crystal X-ray structure of each complex has been determined. The FeII compound, 2, and a mixed valence FeII-FeIII compound, 3, involve formally hemi-deprotonated ligands, H1.5L. The structure of 3 consists of a homochiral two-dimensional assembled sheet, arising from the intermolecular hydrogen bonds between [FeII(H3L)]2+ and [FeIII(L)]0 (3). All but 5 exhibit spin crossover between low-spin (LS) and high-spin (HS) states. This is a rare case where both Fe II and FeIII complexes containing the same ligand exhibit spin-crossover behavior. Magnetic susceptibility and Mössbauer studies showed that 3 has three accessible electronic states: LS FeII-LS FeIII, HS FeII-LS FeIII, and HS Fe II-HS FeIII. Compounds 1-3 show the light-induced excited spin-state trapping effect at the FeII sites upon irradiation with green light. The solution magnetic properties, electronic spectra, and electrochemical properties of 1, 4, and 5 were also studied.

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