Exchange Coupling in an Isostructural Series of Face-Sharing Bioctahedral Complexes [LMII(μ-X)3MIIL]BPh4 M = Mn, Fe, Co, Ni, Zn; X = Cl, Br; L = 1,4,7-Trimethyl-1,4,7-triazacyclononane

Ursula Bossek, Daniela Nühlen, Eckhard Bill, Thorsten Glaser, Carsten Krebs, Thomas Weyhermüller, Karl Wieghardt, Marek Lengen, A. X. Trautwein

Research output: Contribution to journalArticle

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Abstract

The reaction of the divalent metal halides ZnCl2, ZnBr2, MnCl2·CH3CN, MnBr2, FeCl·4CH3CN, CoCl24CH3CN, CoBr2, NiCl2·6H2O, and NiBr2, respectively, with the macrocycle 1,4,7-trimethyl-1,4,7-triazacyclononane (L) (1:1) in anhydrous acetonitrile, acetone, chloroform, or ethanol affords upon additon of NaBPh4 the isomorphous series of complexes [LMII(μ-X)3MIIL]BPh4: 1, M = Zn, X = Cl; 2, Zn, Br; 3, Mn, Cl; 4, Mn, Br; 5, Fe, Cl: 6, Co, Cl; 7, Co, Br; 8, Ni, Cl; 9, Ni, Br. Six of these complexes have been structurally characterized by single-Crystal X-ray crystallography; they crystallize in the triclinic space group P1̄ (No. 2) with Z = 4. Crystal data are as follows 1, a = 16.654(1), b = 17.042(1), c = 17.684(1) Å, α = 97.30(1). β= 93.58(1), γ = 117.46(1)°; 3, a = 16.632(8), b = 17.012(8), c = 17.855(5) Å, α = 97.16(3), β= 93.37(3), γ = 117.24(3)°; 5, a = 16.658(3), b = 17.064(3), c = 17.741(4) Å, α = 97.32(3), β= 93.47(3), γ = 117.36(3)°; 6, a = 16.640(3), b = 17.040(3), c = 17.686(4) Å, α = 97.39(3), β= 93.58(3), γ = 117.39(3)°; 8, a = 16.608(3). b = 16.995(3), c = 17.555(3) Å, α = 97.36(1), β= 93.52(1), γ = 117.52(1)°; 9, a = 16.680(3), b = 17.016(2), c = 17.715(3)Å, α = 96.99(1). β= 93.70(1), γ = 117.42(1)°, All complexes consist of a dinuclear, face-sharing bioctahedral monocation with three μ2-Cl or μ2-Br bridging ligands and two LM fragments and well-separated tetraphenylborate anions (1:1). The cations cocrystallize in two different forms: an enantiomeric form with (λλλ) (or (δδδ)) conformation at both LM fragments and a meso form with an (λλλ) conformation at one LM fragment and (δδδ) at the other (ratio 1:1). From temperature-dependent magnetic susceptibility measurements (2-293 K) it was established that the spins of the unpaired electrons in 3 (d5d5 high spin), 4 (d5d5), 6 (d7d7 high spin), 7 (d7d7), 8 (d8d8), and 9 (d8d8) are intramolecularly, weakly antiferromagnetically coupled in each case, Surprisingly, the spins order ferromagnetically in 5 (d6d6 high spin). This is in contrast to the previously reported complex [(thf)3FeII(μ-Cl)3FeII(thf) 3][SnCl5(thf)] (thf = tetrahydrofuran)5 for which a new analysis of the temperature-dependence of the magnetic susceptibility and of field-dependent Mössbauer spectra establish a weak intramolecular antiferromagnetic coupling. The origin of this difference is analyzed.

Original languageEnglish (US)
Pages (from-to)2834-2843
Number of pages10
JournalInorganic Chemistry
Volume36
Issue number13
StatePublished - Dec 1 1997

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Exchange coupling
Magnetic susceptibility
Conformations
Tetraphenylborate
Metal halides
X ray crystallography
Chloroform
Acetone
Anions
fragments
Cations
Ethanol
Single crystals
Ligands
Temperature
Crystals
Electrons
magnetic permeability
metal halides
tetrahydrofuran

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

Bossek, Ursula ; Nühlen, Daniela ; Bill, Eckhard ; Glaser, Thorsten ; Krebs, Carsten ; Weyhermüller, Thomas ; Wieghardt, Karl ; Lengen, Marek ; Trautwein, A. X. / Exchange Coupling in an Isostructural Series of Face-Sharing Bioctahedral Complexes [LMII(μ-X)3MIIL]BPh4 M = Mn, Fe, Co, Ni, Zn; X = Cl, Br; L = 1,4,7-Trimethyl-1,4,7-triazacyclononane. In: Inorganic Chemistry. 1997 ; Vol. 36, No. 13. pp. 2834-2843.
@article{057cc14815fa42aba0b2fe5da57c8372,
title = "Exchange Coupling in an Isostructural Series of Face-Sharing Bioctahedral Complexes [LMII(μ-X)3MIIL]BPh4 M = Mn, Fe, Co, Ni, Zn; X = Cl, Br; L = 1,4,7-Trimethyl-1,4,7-triazacyclononane",
abstract = "The reaction of the divalent metal halides ZnCl2, ZnBr2, MnCl2·CH3CN, MnBr2, FeCl·4CH3CN, CoCl24CH3CN, CoBr2, NiCl2·6H2O, and NiBr2, respectively, with the macrocycle 1,4,7-trimethyl-1,4,7-triazacyclononane (L) (1:1) in anhydrous acetonitrile, acetone, chloroform, or ethanol affords upon additon of NaBPh4 the isomorphous series of complexes [LMII(μ-X)3MIIL]BPh4: 1, M = Zn, X = Cl; 2, Zn, Br; 3, Mn, Cl; 4, Mn, Br; 5, Fe, Cl: 6, Co, Cl; 7, Co, Br; 8, Ni, Cl; 9, Ni, Br. Six of these complexes have been structurally characterized by single-Crystal X-ray crystallography; they crystallize in the triclinic space group P1̄ (No. 2) with Z = 4. Crystal data are as follows 1, a = 16.654(1), b = 17.042(1), c = 17.684(1) {\AA}, α = 97.30(1). β= 93.58(1), γ = 117.46(1)°; 3, a = 16.632(8), b = 17.012(8), c = 17.855(5) {\AA}, α = 97.16(3), β= 93.37(3), γ = 117.24(3)°; 5, a = 16.658(3), b = 17.064(3), c = 17.741(4) {\AA}, α = 97.32(3), β= 93.47(3), γ = 117.36(3)°; 6, a = 16.640(3), b = 17.040(3), c = 17.686(4) {\AA}, α = 97.39(3), β= 93.58(3), γ = 117.39(3)°; 8, a = 16.608(3). b = 16.995(3), c = 17.555(3) {\AA}, α = 97.36(1), β= 93.52(1), γ = 117.52(1)°; 9, a = 16.680(3), b = 17.016(2), c = 17.715(3){\AA}, α = 96.99(1). β= 93.70(1), γ = 117.42(1)°, All complexes consist of a dinuclear, face-sharing bioctahedral monocation with three μ2-Cl or μ2-Br bridging ligands and two LM fragments and well-separated tetraphenylborate anions (1:1). The cations cocrystallize in two different forms: an enantiomeric form with (λλλ) (or (δδδ)) conformation at both LM fragments and a meso form with an (λλλ) conformation at one LM fragment and (δδδ) at the other (ratio 1:1). From temperature-dependent magnetic susceptibility measurements (2-293 K) it was established that the spins of the unpaired electrons in 3 (d5d5 high spin), 4 (d5d5), 6 (d7d7 high spin), 7 (d7d7), 8 (d8d8), and 9 (d8d8) are intramolecularly, weakly antiferromagnetically coupled in each case, Surprisingly, the spins order ferromagnetically in 5 (d6d6 high spin). This is in contrast to the previously reported complex [(thf)3FeII(μ-Cl)3FeII(thf) 3][SnCl5(thf)] (thf = tetrahydrofuran)5 for which a new analysis of the temperature-dependence of the magnetic susceptibility and of field-dependent M{\"o}ssbauer spectra establish a weak intramolecular antiferromagnetic coupling. The origin of this difference is analyzed.",
author = "Ursula Bossek and Daniela N{\"u}hlen and Eckhard Bill and Thorsten Glaser and Carsten Krebs and Thomas Weyherm{\"u}ller and Karl Wieghardt and Marek Lengen and Trautwein, {A. X.}",
year = "1997",
month = "12",
day = "1",
language = "English (US)",
volume = "36",
pages = "2834--2843",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "13",

}

Bossek, U, Nühlen, D, Bill, E, Glaser, T, Krebs, C, Weyhermüller, T, Wieghardt, K, Lengen, M & Trautwein, AX 1997, 'Exchange Coupling in an Isostructural Series of Face-Sharing Bioctahedral Complexes [LMII(μ-X)3MIIL]BPh4 M = Mn, Fe, Co, Ni, Zn; X = Cl, Br; L = 1,4,7-Trimethyl-1,4,7-triazacyclononane', Inorganic Chemistry, vol. 36, no. 13, pp. 2834-2843.

Exchange Coupling in an Isostructural Series of Face-Sharing Bioctahedral Complexes [LMII(μ-X)3MIIL]BPh4 M = Mn, Fe, Co, Ni, Zn; X = Cl, Br; L = 1,4,7-Trimethyl-1,4,7-triazacyclononane. / Bossek, Ursula; Nühlen, Daniela; Bill, Eckhard; Glaser, Thorsten; Krebs, Carsten; Weyhermüller, Thomas; Wieghardt, Karl; Lengen, Marek; Trautwein, A. X.

In: Inorganic Chemistry, Vol. 36, No. 13, 01.12.1997, p. 2834-2843.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Exchange Coupling in an Isostructural Series of Face-Sharing Bioctahedral Complexes [LMII(μ-X)3MIIL]BPh4 M = Mn, Fe, Co, Ni, Zn; X = Cl, Br; L = 1,4,7-Trimethyl-1,4,7-triazacyclononane

AU - Bossek, Ursula

AU - Nühlen, Daniela

AU - Bill, Eckhard

AU - Glaser, Thorsten

AU - Krebs, Carsten

AU - Weyhermüller, Thomas

AU - Wieghardt, Karl

AU - Lengen, Marek

AU - Trautwein, A. X.

PY - 1997/12/1

Y1 - 1997/12/1

N2 - The reaction of the divalent metal halides ZnCl2, ZnBr2, MnCl2·CH3CN, MnBr2, FeCl·4CH3CN, CoCl24CH3CN, CoBr2, NiCl2·6H2O, and NiBr2, respectively, with the macrocycle 1,4,7-trimethyl-1,4,7-triazacyclononane (L) (1:1) in anhydrous acetonitrile, acetone, chloroform, or ethanol affords upon additon of NaBPh4 the isomorphous series of complexes [LMII(μ-X)3MIIL]BPh4: 1, M = Zn, X = Cl; 2, Zn, Br; 3, Mn, Cl; 4, Mn, Br; 5, Fe, Cl: 6, Co, Cl; 7, Co, Br; 8, Ni, Cl; 9, Ni, Br. Six of these complexes have been structurally characterized by single-Crystal X-ray crystallography; they crystallize in the triclinic space group P1̄ (No. 2) with Z = 4. Crystal data are as follows 1, a = 16.654(1), b = 17.042(1), c = 17.684(1) Å, α = 97.30(1). β= 93.58(1), γ = 117.46(1)°; 3, a = 16.632(8), b = 17.012(8), c = 17.855(5) Å, α = 97.16(3), β= 93.37(3), γ = 117.24(3)°; 5, a = 16.658(3), b = 17.064(3), c = 17.741(4) Å, α = 97.32(3), β= 93.47(3), γ = 117.36(3)°; 6, a = 16.640(3), b = 17.040(3), c = 17.686(4) Å, α = 97.39(3), β= 93.58(3), γ = 117.39(3)°; 8, a = 16.608(3). b = 16.995(3), c = 17.555(3) Å, α = 97.36(1), β= 93.52(1), γ = 117.52(1)°; 9, a = 16.680(3), b = 17.016(2), c = 17.715(3)Å, α = 96.99(1). β= 93.70(1), γ = 117.42(1)°, All complexes consist of a dinuclear, face-sharing bioctahedral monocation with three μ2-Cl or μ2-Br bridging ligands and two LM fragments and well-separated tetraphenylborate anions (1:1). The cations cocrystallize in two different forms: an enantiomeric form with (λλλ) (or (δδδ)) conformation at both LM fragments and a meso form with an (λλλ) conformation at one LM fragment and (δδδ) at the other (ratio 1:1). From temperature-dependent magnetic susceptibility measurements (2-293 K) it was established that the spins of the unpaired electrons in 3 (d5d5 high spin), 4 (d5d5), 6 (d7d7 high spin), 7 (d7d7), 8 (d8d8), and 9 (d8d8) are intramolecularly, weakly antiferromagnetically coupled in each case, Surprisingly, the spins order ferromagnetically in 5 (d6d6 high spin). This is in contrast to the previously reported complex [(thf)3FeII(μ-Cl)3FeII(thf) 3][SnCl5(thf)] (thf = tetrahydrofuran)5 for which a new analysis of the temperature-dependence of the magnetic susceptibility and of field-dependent Mössbauer spectra establish a weak intramolecular antiferromagnetic coupling. The origin of this difference is analyzed.

AB - The reaction of the divalent metal halides ZnCl2, ZnBr2, MnCl2·CH3CN, MnBr2, FeCl·4CH3CN, CoCl24CH3CN, CoBr2, NiCl2·6H2O, and NiBr2, respectively, with the macrocycle 1,4,7-trimethyl-1,4,7-triazacyclononane (L) (1:1) in anhydrous acetonitrile, acetone, chloroform, or ethanol affords upon additon of NaBPh4 the isomorphous series of complexes [LMII(μ-X)3MIIL]BPh4: 1, M = Zn, X = Cl; 2, Zn, Br; 3, Mn, Cl; 4, Mn, Br; 5, Fe, Cl: 6, Co, Cl; 7, Co, Br; 8, Ni, Cl; 9, Ni, Br. Six of these complexes have been structurally characterized by single-Crystal X-ray crystallography; they crystallize in the triclinic space group P1̄ (No. 2) with Z = 4. Crystal data are as follows 1, a = 16.654(1), b = 17.042(1), c = 17.684(1) Å, α = 97.30(1). β= 93.58(1), γ = 117.46(1)°; 3, a = 16.632(8), b = 17.012(8), c = 17.855(5) Å, α = 97.16(3), β= 93.37(3), γ = 117.24(3)°; 5, a = 16.658(3), b = 17.064(3), c = 17.741(4) Å, α = 97.32(3), β= 93.47(3), γ = 117.36(3)°; 6, a = 16.640(3), b = 17.040(3), c = 17.686(4) Å, α = 97.39(3), β= 93.58(3), γ = 117.39(3)°; 8, a = 16.608(3). b = 16.995(3), c = 17.555(3) Å, α = 97.36(1), β= 93.52(1), γ = 117.52(1)°; 9, a = 16.680(3), b = 17.016(2), c = 17.715(3)Å, α = 96.99(1). β= 93.70(1), γ = 117.42(1)°, All complexes consist of a dinuclear, face-sharing bioctahedral monocation with three μ2-Cl or μ2-Br bridging ligands and two LM fragments and well-separated tetraphenylborate anions (1:1). The cations cocrystallize in two different forms: an enantiomeric form with (λλλ) (or (δδδ)) conformation at both LM fragments and a meso form with an (λλλ) conformation at one LM fragment and (δδδ) at the other (ratio 1:1). From temperature-dependent magnetic susceptibility measurements (2-293 K) it was established that the spins of the unpaired electrons in 3 (d5d5 high spin), 4 (d5d5), 6 (d7d7 high spin), 7 (d7d7), 8 (d8d8), and 9 (d8d8) are intramolecularly, weakly antiferromagnetically coupled in each case, Surprisingly, the spins order ferromagnetically in 5 (d6d6 high spin). This is in contrast to the previously reported complex [(thf)3FeII(μ-Cl)3FeII(thf) 3][SnCl5(thf)] (thf = tetrahydrofuran)5 for which a new analysis of the temperature-dependence of the magnetic susceptibility and of field-dependent Mössbauer spectra establish a weak intramolecular antiferromagnetic coupling. The origin of this difference is analyzed.

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