Ground spin state variation in carboxylate-bridged tetranuclear [Fe2Mn2O2]8+ cores and a comparison with their [Fe4O2]8+ and [Mn4O2]18+ congeners

Phalguni Chaudhuri, Eva Rentschler, Frank Birkelbach, Carsten Krebs, Eckhard Bill, Thomas Weyhermüller, Ulrich Flörke

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Abstract

Syntheses of ten new tetranuclear complexes containing the [MA3-O)2MB]8+ butterfly core [MA = MB = FeIII (1 and 2), MA = MB = MnIII (3 and 4) and MA = FeIII, MB = MnIII (5-10)] using 1,4,7-trimethyl-1,4,7-triazacyclononane (L) as the capping ligand, salicylaldoximato dianion (salox2-) and six different carboxylate anions as bridging ligands, are described. The crystal structures of [L2Fe23-O)2 (salox)2(diphenylglycolate)3Fe2] (ClO4) (1), [L2Mn23-O)2 (salox)2(diphenylglycolate)3Mn2] (ClO4) (3), [L2Fe23-O)2 (salox)2(acetate)3Mn2]- (ClO4) (5), [L2Fe23-O)2 (salox)2(diphenylglycolate)3Mn2]- (ClO4) (6), and [L2Fe23-O)2 (salox)2(benzoate)3Mn2]- (ClO4) (8) were determined by X-ray crystallography. The complexes are isostructural, with MIII ions disposed in a butterfly core where bridging between the MIII ions occurs via two μ3-oxo anions. In complexes 5, 6 and 8 the "wing-tip" positions of the butterfly are occupied by the LFe3+ units, whereas the "body" metal ions are d4 high-spin MnIII ions. Complexes 1-10 have been characterised by variable-temperature (2-290 K) magnetic susceptibility measurements (1 T) and by Mössbauer spectroscopy. A "2J" model has been applied to simulate the experimental μeff vs. T plots. Overall exchange interactions are antiferromagnetic in nature. Complexes with the Fe4O2 core (1 and 2) and the Mn4O2 core (3 and 4) possess an St = 0 and St = 3 ground state, respectively, regardless of the nature of the bridging carboxylate ligand. In contrast, changing the bridging carboxylates in the [Fe2Mn2O2] core from acetate (5) to diphenylglycolate (6), triphenyl acetate (7), benzoate (8), chloroacetate (9) and propionate (10), results in a variation of the ground state from St = 1 to St = 3, due to spin frustration of the "body" manganese centres. The spin-correlation diagram for the Fe2Mn2O2 butterfly arrangement clearly demonstrates the ground state variation as a function of the ratio of two competing coupling interactions.

Original languageEnglish (US)
Pages (from-to)541-555
Number of pages15
JournalEuropean Journal of Inorganic Chemistry
Issue number3
DOIs
StatePublished - Jan 1 2003

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Ground state
Acetates
Benzoates
Ions
Ligands
Anions
X ray crystallography
Exchange interactions
Propionates
Manganese
Magnetic susceptibility
Metal ions
Crystal structure
perchlorate
Spectroscopy
Temperature
MB 3
chloroacetic acid
1,4,7-trimethyl-1,4,7-triazacyclononane
7-hydroxy-6-methoxyphthalide

All Science Journal Classification (ASJC) codes

  • Inorganic Chemistry

Cite this

Chaudhuri, Phalguni ; Rentschler, Eva ; Birkelbach, Frank ; Krebs, Carsten ; Bill, Eckhard ; Weyhermüller, Thomas ; Flörke, Ulrich. / Ground spin state variation in carboxylate-bridged tetranuclear [Fe2Mn2O2]8+ cores and a comparison with their [Fe4O2]8+ and [Mn4O2]18+ congeners. In: European Journal of Inorganic Chemistry. 2003 ; No. 3. pp. 541-555.
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abstract = "Syntheses of ten new tetranuclear complexes containing the [MA(μ3-O)2MB]8+ butterfly core [MA = MB = FeIII (1 and 2), MA = MB = MnIII (3 and 4) and MA = FeIII, MB = MnIII (5-10)] using 1,4,7-trimethyl-1,4,7-triazacyclononane (L) as the capping ligand, salicylaldoximato dianion (salox2-) and six different carboxylate anions as bridging ligands, are described. The crystal structures of [L2Fe2(μ3-O)2 (salox)2(diphenylglycolate)3Fe2] (ClO4) (1), [L2Mn2(μ3-O)2 (salox)2(diphenylglycolate)3Mn2] (ClO4) (3), [L2Fe2(μ3-O)2 (salox)2(acetate)3Mn2]- (ClO4) (5), [L2Fe2(μ3-O)2 (salox)2(diphenylglycolate)3Mn2]- (ClO4) (6), and [L2Fe2(μ3-O)2 (salox)2(benzoate)3Mn2]- (ClO4) (8) were determined by X-ray crystallography. The complexes are isostructural, with MIII ions disposed in a butterfly core where bridging between the MIII ions occurs via two μ3-oxo anions. In complexes 5, 6 and 8 the {"}wing-tip{"} positions of the butterfly are occupied by the LFe3+ units, whereas the {"}body{"} metal ions are d4 high-spin MnIII ions. Complexes 1-10 have been characterised by variable-temperature (2-290 K) magnetic susceptibility measurements (1 T) and by M{\"o}ssbauer spectroscopy. A {"}2J{"} model has been applied to simulate the experimental μeff vs. T plots. Overall exchange interactions are antiferromagnetic in nature. Complexes with the Fe4O2 core (1 and 2) and the Mn4O2 core (3 and 4) possess an St = 0 and St = 3 ground state, respectively, regardless of the nature of the bridging carboxylate ligand. In contrast, changing the bridging carboxylates in the [Fe2Mn2O2] core from acetate (5) to diphenylglycolate (6), triphenyl acetate (7), benzoate (8), chloroacetate (9) and propionate (10), results in a variation of the ground state from St = 1 to St = 3, due to spin frustration of the {"}body{"} manganese centres. The spin-correlation diagram for the Fe2Mn2O2 butterfly arrangement clearly demonstrates the ground state variation as a function of the ratio of two competing coupling interactions.",
author = "Phalguni Chaudhuri and Eva Rentschler and Frank Birkelbach and Carsten Krebs and Eckhard Bill and Thomas Weyherm{\"u}ller and Ulrich Fl{\"o}rke",
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Ground spin state variation in carboxylate-bridged tetranuclear [Fe2Mn2O2]8+ cores and a comparison with their [Fe4O2]8+ and [Mn4O2]18+ congeners. / Chaudhuri, Phalguni; Rentschler, Eva; Birkelbach, Frank; Krebs, Carsten; Bill, Eckhard; Weyhermüller, Thomas; Flörke, Ulrich.

In: European Journal of Inorganic Chemistry, No. 3, 01.01.2003, p. 541-555.

Research output: Contribution to journalArticle

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T1 - Ground spin state variation in carboxylate-bridged tetranuclear [Fe2Mn2O2]8+ cores and a comparison with their [Fe4O2]8+ and [Mn4O2]18+ congeners

AU - Chaudhuri, Phalguni

AU - Rentschler, Eva

AU - Birkelbach, Frank

AU - Krebs, Carsten

AU - Bill, Eckhard

AU - Weyhermüller, Thomas

AU - Flörke, Ulrich

PY - 2003/1/1

Y1 - 2003/1/1

N2 - Syntheses of ten new tetranuclear complexes containing the [MA(μ3-O)2MB]8+ butterfly core [MA = MB = FeIII (1 and 2), MA = MB = MnIII (3 and 4) and MA = FeIII, MB = MnIII (5-10)] using 1,4,7-trimethyl-1,4,7-triazacyclononane (L) as the capping ligand, salicylaldoximato dianion (salox2-) and six different carboxylate anions as bridging ligands, are described. The crystal structures of [L2Fe2(μ3-O)2 (salox)2(diphenylglycolate)3Fe2] (ClO4) (1), [L2Mn2(μ3-O)2 (salox)2(diphenylglycolate)3Mn2] (ClO4) (3), [L2Fe2(μ3-O)2 (salox)2(acetate)3Mn2]- (ClO4) (5), [L2Fe2(μ3-O)2 (salox)2(diphenylglycolate)3Mn2]- (ClO4) (6), and [L2Fe2(μ3-O)2 (salox)2(benzoate)3Mn2]- (ClO4) (8) were determined by X-ray crystallography. The complexes are isostructural, with MIII ions disposed in a butterfly core where bridging between the MIII ions occurs via two μ3-oxo anions. In complexes 5, 6 and 8 the "wing-tip" positions of the butterfly are occupied by the LFe3+ units, whereas the "body" metal ions are d4 high-spin MnIII ions. Complexes 1-10 have been characterised by variable-temperature (2-290 K) magnetic susceptibility measurements (1 T) and by Mössbauer spectroscopy. A "2J" model has been applied to simulate the experimental μeff vs. T plots. Overall exchange interactions are antiferromagnetic in nature. Complexes with the Fe4O2 core (1 and 2) and the Mn4O2 core (3 and 4) possess an St = 0 and St = 3 ground state, respectively, regardless of the nature of the bridging carboxylate ligand. In contrast, changing the bridging carboxylates in the [Fe2Mn2O2] core from acetate (5) to diphenylglycolate (6), triphenyl acetate (7), benzoate (8), chloroacetate (9) and propionate (10), results in a variation of the ground state from St = 1 to St = 3, due to spin frustration of the "body" manganese centres. The spin-correlation diagram for the Fe2Mn2O2 butterfly arrangement clearly demonstrates the ground state variation as a function of the ratio of two competing coupling interactions.

AB - Syntheses of ten new tetranuclear complexes containing the [MA(μ3-O)2MB]8+ butterfly core [MA = MB = FeIII (1 and 2), MA = MB = MnIII (3 and 4) and MA = FeIII, MB = MnIII (5-10)] using 1,4,7-trimethyl-1,4,7-triazacyclononane (L) as the capping ligand, salicylaldoximato dianion (salox2-) and six different carboxylate anions as bridging ligands, are described. The crystal structures of [L2Fe2(μ3-O)2 (salox)2(diphenylglycolate)3Fe2] (ClO4) (1), [L2Mn2(μ3-O)2 (salox)2(diphenylglycolate)3Mn2] (ClO4) (3), [L2Fe2(μ3-O)2 (salox)2(acetate)3Mn2]- (ClO4) (5), [L2Fe2(μ3-O)2 (salox)2(diphenylglycolate)3Mn2]- (ClO4) (6), and [L2Fe2(μ3-O)2 (salox)2(benzoate)3Mn2]- (ClO4) (8) were determined by X-ray crystallography. The complexes are isostructural, with MIII ions disposed in a butterfly core where bridging between the MIII ions occurs via two μ3-oxo anions. In complexes 5, 6 and 8 the "wing-tip" positions of the butterfly are occupied by the LFe3+ units, whereas the "body" metal ions are d4 high-spin MnIII ions. Complexes 1-10 have been characterised by variable-temperature (2-290 K) magnetic susceptibility measurements (1 T) and by Mössbauer spectroscopy. A "2J" model has been applied to simulate the experimental μeff vs. T plots. Overall exchange interactions are antiferromagnetic in nature. Complexes with the Fe4O2 core (1 and 2) and the Mn4O2 core (3 and 4) possess an St = 0 and St = 3 ground state, respectively, regardless of the nature of the bridging carboxylate ligand. In contrast, changing the bridging carboxylates in the [Fe2Mn2O2] core from acetate (5) to diphenylglycolate (6), triphenyl acetate (7), benzoate (8), chloroacetate (9) and propionate (10), results in a variation of the ground state from St = 1 to St = 3, due to spin frustration of the "body" manganese centres. The spin-correlation diagram for the Fe2Mn2O2 butterfly arrangement clearly demonstrates the ground state variation as a function of the ratio of two competing coupling interactions.

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