Synthesis, crystal structure, EXAFS, and magnetic properties of catena [μ-tris(1,2-bis(tetrazol-1-yl)propane-N1,N1')iron(II)] bis(perchlorate).: First crystal structure of an iron(II) spin-crossover chain compound

Petra J.  van Koningsbruggen; Yann Garcia; Olivier Kahn; Léopold Fournès; Huub Kooijman; Anghony L Spek; Jaap G. Haasnoot; Jacques Moscovici; Karine Provost; Alain Michalowicz; Franz Renz; Philipp Gütlich

doi:10.1021/ic991118n

Synthesis, crystal structure, EXAFS, and magnetic properties of catena [μ-tris(1,2-bis(tetrazol-1-yl)propane-N1,N1')iron(II)] bis(perchlorate). First crystal structure of an iron(II) spin-crossover chain compound

Petra J. van Koningsbruggen, Yann Garcia, Olivier Kahn, Léopold Fournès, Huub Kooijman, Anghony L Spek, Jaap G. Haasnoot, Jacques Moscovici, Karine Provost, Alain Michalowicz, Franz Renz, Philipp Gütlich

Chemical Engineering & Applied Chemistry

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Abstract

[Fe(btzp)₃](ClO₄)₂ (btzp = 1,2-bis(tetrazol-1-yl)propane) represents the first structurally characterized Fe(II) linear chain compound exhibiting thermal spin crossover. It shows a very gradual spin transition (T_1/2 = 130 K) which has been followed by magnetic susceptibility measurements and ⁵⁷Fe Mössbauer spectroscopy. The structure has been solved at 200 and 100 K by single-crystal X-ray analysis. It crystallizes in the trigonal space group P3c1 with Z = 2 Fe(II) units at both temperatures. The molecular structure consists of chains running along the c axis in which the Fe(II) ions are linked by three N4,N4' coordinating bis(tetrazole) ligands. The main difference between the two forms appears to be in the Fe-N bond lengths, which are 2.164(4) A at 200 K and 2.038(4) A at 100 K. The Fe-Fe separations are 7.422(1) Å at 200 K and 7.273(1) A at 100 K. The EXAFS results are consistent with the crystal structure. In both spin states, the FeN6 octahedron is almost regular within the EXAFS resolution. The Fe-N distance is found as 2.16(2)Åat 300 K and 2.00(2) Å at 40 K. The absence of the "7 Å peak" in the EXAFS spectra of [Fe(btzp)₃](ClO₄)₂, in contrast with what has been observed for the [Fe(4-R-1,2,4-triazole)₃]-(anion)₂ chain compounds, confirms that this peak can be used as the signature of a metal alignment only when it involves a strongly enhanced multiple scattering M-M-M path, with M-M spacing less than 4 A. Irradiation with green light at 5 K has led to the population of the metastable high-spin state for the iron(II) ion. The nature of the spin-crossover behavior has been discussed on the basis of the structural features.

Original language	English
Pages (from-to)	1891-1900
Number of pages	10
Journal	Inorganic Chemistry
Volume	39
Issue number	9
DOIs	https://doi.org/10.1021/ic991118n
Publication status	Published - 1 May 2000

Keywords

Anions
Ligands
Ions
Extended X-ray absorption fine structure
Quantum mechanics

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van Koningsbruggen, P. J., Garcia, Y., Kahn, O., Fournès, L., Kooijman, H., Spek, A. L., Haasnoot, J. G., Moscovici, J., Provost, K., Michalowicz, A., Renz, F., & Gütlich, P. (2000). Synthesis, crystal structure, EXAFS, and magnetic properties of catena [μ-tris(1,2-bis(tetrazol-1-yl)propane-N1,N1')iron(II)] bis(perchlorate). First crystal structure of an iron(II) spin-crossover chain compound. Inorganic Chemistry, 39(9), 1891-1900. https://doi.org/10.1021/ic991118n

@article{877318408e3b410e9386405a7f3d36b2,

title = "Synthesis, crystal structure, EXAFS, and magnetic properties of catena [μ-tris(1,2-bis(tetrazol-1-yl)propane-N1,N1')iron(II)] bis(perchlorate).: First crystal structure of an iron(II) spin-crossover chain compound",

abstract = "[Fe(btzp)3](ClO4)2 (btzp = 1,2-bis(tetrazol-1-yl)propane) represents the first structurally characterized Fe(II) linear chain compound exhibiting thermal spin crossover. It shows a very gradual spin transition (T1/2 = 130 K) which has been followed by magnetic susceptibility measurements and 57Fe M{\"o}ssbauer spectroscopy. The structure has been solved at 200 and 100 K by single-crystal X-ray analysis. It crystallizes in the trigonal space group P3c1 with Z = 2 Fe(II) units at both temperatures. The molecular structure consists of chains running along the c axis in which the Fe(II) ions are linked by three N4,N4' coordinating bis(tetrazole) ligands. The main difference between the two forms appears to be in the Fe-N bond lengths, which are 2.164(4) A at 200 K and 2.038(4) A at 100 K. The Fe-Fe separations are 7.422(1) {\AA} at 200 K and 7.273(1) A at 100 K. The EXAFS results are consistent with the crystal structure. In both spin states, the FeN6 octahedron is almost regular within the EXAFS resolution. The Fe-N distance is found as 2.16(2){\AA}at 300 K and 2.00(2) {\AA} at 40 K. The absence of the {"}7 {\AA} peak{"} in the EXAFS spectra of [Fe(btzp)3](ClO4)2, in contrast with what has been observed for the [Fe(4-R-1,2,4-triazole)3]-(anion)2 chain compounds, confirms that this peak can be used as the signature of a metal alignment only when it involves a strongly enhanced multiple scattering M-M-M path, with M-M spacing less than 4 A. Irradiation with green light at 5 K has led to the population of the metastable high-spin state for the iron(II) ion. The nature of the spin-crossover behavior has been discussed on the basis of the structural features.",

keywords = "Anions, Ligands, Ions, Extended X-ray absorption fine structure, Quantum mechanics",

author = "{van Koningsbruggen}, {Petra J.} and Yann Garcia and Olivier Kahn and L{\'e}opold Fourn{\`e}s and Huub Kooijman and Spek, {Anghony L} and Haasnoot, {Jaap G.} and Jacques Moscovici and Karine Provost and Alain Michalowicz and Franz Renz and Philipp G{\"u}tlich",

year = "2000",

month = may,

day = "1",

doi = "10.1021/ic991118n",

language = "English",

volume = "39",

pages = "1891--1900",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "9",

}

van Koningsbruggen, PJ, Garcia, Y, Kahn, O, Fournès, L, Kooijman, H, Spek, AL, Haasnoot, JG, Moscovici, J, Provost, K, Michalowicz, A, Renz, F & Gütlich, P 2000, 'Synthesis, crystal structure, EXAFS, and magnetic properties of catena [μ-tris(1,2-bis(tetrazol-1-yl)propane-N1,N1')iron(II)] bis(perchlorate). First crystal structure of an iron(II) spin-crossover chain compound', Inorganic Chemistry, vol. 39, no. 9, pp. 1891-1900. https://doi.org/10.1021/ic991118n

Synthesis, crystal structure, EXAFS, and magnetic properties of catena [μ-tris(1,2-bis(tetrazol-1-yl)propane-N1,N1')iron(II)] bis(perchlorate). First crystal structure of an iron(II) spin-crossover chain compound. / van Koningsbruggen, Petra J. ; Garcia, Yann; Kahn, Olivier et al.
In: Inorganic Chemistry, Vol. 39, No. 9, 01.05.2000, p. 1891-1900.

Research output: Contribution to journal › Article › peer-review

TY - JOUR

T1 - Synthesis, crystal structure, EXAFS, and magnetic properties of catena [μ-tris(1,2-bis(tetrazol-1-yl)propane-N1,N1')iron(II)] bis(perchlorate).

T2 - First crystal structure of an iron(II) spin-crossover chain compound

AU - van Koningsbruggen, Petra J.

AU - Garcia, Yann

AU - Kahn, Olivier

AU - Fournès, Léopold

AU - Kooijman, Huub

AU - Spek, Anghony L

AU - Haasnoot, Jaap G.

AU - Moscovici, Jacques

AU - Provost, Karine

AU - Michalowicz, Alain

AU - Renz, Franz

AU - Gütlich, Philipp

PY - 2000/5/1

Y1 - 2000/5/1

N2 - [Fe(btzp)3](ClO4)2 (btzp = 1,2-bis(tetrazol-1-yl)propane) represents the first structurally characterized Fe(II) linear chain compound exhibiting thermal spin crossover. It shows a very gradual spin transition (T1/2 = 130 K) which has been followed by magnetic susceptibility measurements and 57Fe Mössbauer spectroscopy. The structure has been solved at 200 and 100 K by single-crystal X-ray analysis. It crystallizes in the trigonal space group P3c1 with Z = 2 Fe(II) units at both temperatures. The molecular structure consists of chains running along the c axis in which the Fe(II) ions are linked by three N4,N4' coordinating bis(tetrazole) ligands. The main difference between the two forms appears to be in the Fe-N bond lengths, which are 2.164(4) A at 200 K and 2.038(4) A at 100 K. The Fe-Fe separations are 7.422(1) Å at 200 K and 7.273(1) A at 100 K. The EXAFS results are consistent with the crystal structure. In both spin states, the FeN6 octahedron is almost regular within the EXAFS resolution. The Fe-N distance is found as 2.16(2)Åat 300 K and 2.00(2) Å at 40 K. The absence of the "7 Å peak" in the EXAFS spectra of [Fe(btzp)3](ClO4)2, in contrast with what has been observed for the [Fe(4-R-1,2,4-triazole)3]-(anion)2 chain compounds, confirms that this peak can be used as the signature of a metal alignment only when it involves a strongly enhanced multiple scattering M-M-M path, with M-M spacing less than 4 A. Irradiation with green light at 5 K has led to the population of the metastable high-spin state for the iron(II) ion. The nature of the spin-crossover behavior has been discussed on the basis of the structural features.

AB - [Fe(btzp)3](ClO4)2 (btzp = 1,2-bis(tetrazol-1-yl)propane) represents the first structurally characterized Fe(II) linear chain compound exhibiting thermal spin crossover. It shows a very gradual spin transition (T1/2 = 130 K) which has been followed by magnetic susceptibility measurements and 57Fe Mössbauer spectroscopy. The structure has been solved at 200 and 100 K by single-crystal X-ray analysis. It crystallizes in the trigonal space group P3c1 with Z = 2 Fe(II) units at both temperatures. The molecular structure consists of chains running along the c axis in which the Fe(II) ions are linked by three N4,N4' coordinating bis(tetrazole) ligands. The main difference between the two forms appears to be in the Fe-N bond lengths, which are 2.164(4) A at 200 K and 2.038(4) A at 100 K. The Fe-Fe separations are 7.422(1) Å at 200 K and 7.273(1) A at 100 K. The EXAFS results are consistent with the crystal structure. In both spin states, the FeN6 octahedron is almost regular within the EXAFS resolution. The Fe-N distance is found as 2.16(2)Åat 300 K and 2.00(2) Å at 40 K. The absence of the "7 Å peak" in the EXAFS spectra of [Fe(btzp)3](ClO4)2, in contrast with what has been observed for the [Fe(4-R-1,2,4-triazole)3]-(anion)2 chain compounds, confirms that this peak can be used as the signature of a metal alignment only when it involves a strongly enhanced multiple scattering M-M-M path, with M-M spacing less than 4 A. Irradiation with green light at 5 K has led to the population of the metastable high-spin state for the iron(II) ion. The nature of the spin-crossover behavior has been discussed on the basis of the structural features.

KW - Anions

KW - Ligands

KW - Ions

KW - Extended X-ray absorption fine structure

KW - Quantum mechanics

UR - https://pubs.acs.org/doi/10.1021/ic991118n

U2 - 10.1021/ic991118n

DO - 10.1021/ic991118n

M3 - Article

C2 - 11428109

SN - 0020-1669

VL - 39

SP - 1891

EP - 1900

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 9

ER -