Synthesis, structures and magnetic properties of two hexanuclear complexes

Chen I. Yang, Kai Hung Cheng, Motohiro Nakano, Gene Hsiang Lee, Hui-Lien Tsai

Research output: Contribution to journalArticle

19 Citations (Scopus)

Abstract

The reaction of salicylaldoxime (H2salox) with Mn(ClO4)2 · 6H2O, NaN(CN)2 and NEt3 in MeOH affords a MnIII6 hexanuclear complex of [Mn6O2(salox)6(MeOH)6(NCNCONH2)2] (1), while reaction of H2salox with MnCl2 · 4H2O and NEt4OH in EtOH affords a MnIII6 hexanuclear complex of [Mn6O2(salox)6(EtOH)4(H2O)2Cl2] (2). Both complexes 1 and 2 contain a [MnIII63-O)2]14+ core, which is a known structural type in the family of Mn6 complexes. Variable temperature magnetic susceptibilities and magnetization measurement of complexes 1 and 2 have been carried out. Exchange interactions of metal centers for complexes 1 and 2 are fitted by a full diagonalization matrix method. The fitting results indicate that both complexes 1 and 2 have the ground-state spin value of S = 4, and the ground state of complex 1 has the much closer energy to low-lying spin states than that of complex 2. Magnetization measurements at 2.0-4.0 K and 10-70 kG confirm that the ground state is S = 4, with significant magnetoanisotropy as gauged by the D value of -0.82 cm-1 and -1.18 cm-1, for 1 and 2, respectively. The frequency dependence of the out-of-phase component in alternating current magnetic susceptibilities for both complexes 1 and 2 indicates the slow magnetic relaxation of superparamagnetic behaviour with a Ueff of 27.0(1) K and τ0 = 3.8(2) × 10-9 s for complex 1, and Ueff of 25.1(6) K and τ0 = 4.6(1) × 10-8 s for complex 2.

Original languageEnglish
Pages (from-to)1842-1851
Number of pages10
JournalPolyhedron
Volume28
Issue number9-10
DOIs
Publication statusPublished - 2009 Jun 22

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Ground state
Magnetic properties
magnetic properties
Magnetic susceptibility
ground state
Magnetization
synthesis
Magnetic relaxation
magnetic permeability
magnetization
Exchange interactions
magnetic relaxation
matrix methods
alternating current
Metals
metals
interactions
Temperature
temperature
energy

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

Cite this

Yang, Chen I. ; Cheng, Kai Hung ; Nakano, Motohiro ; Lee, Gene Hsiang ; Tsai, Hui-Lien. / Synthesis, structures and magnetic properties of two hexanuclear complexes. In: Polyhedron. 2009 ; Vol. 28, No. 9-10. pp. 1842-1851.
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abstract = "The reaction of salicylaldoxime (H2salox) with Mn(ClO4)2 · 6H2O, NaN(CN)2 and NEt3 in MeOH affords a MnIII6 hexanuclear complex of [Mn6O2(salox)6(MeOH)6(NCNCONH2)2] (1), while reaction of H2salox with MnCl2 · 4H2O and NEt4OH in EtOH affords a MnIII6 hexanuclear complex of [Mn6O2(salox)6(EtOH)4(H2O)2Cl2] (2). Both complexes 1 and 2 contain a [MnIII6(μ3-O)2]14+ core, which is a known structural type in the family of Mn6 complexes. Variable temperature magnetic susceptibilities and magnetization measurement of complexes 1 and 2 have been carried out. Exchange interactions of metal centers for complexes 1 and 2 are fitted by a full diagonalization matrix method. The fitting results indicate that both complexes 1 and 2 have the ground-state spin value of S = 4, and the ground state of complex 1 has the much closer energy to low-lying spin states than that of complex 2. Magnetization measurements at 2.0-4.0 K and 10-70 kG confirm that the ground state is S = 4, with significant magnetoanisotropy as gauged by the D value of -0.82 cm-1 and -1.18 cm-1, for 1 and 2, respectively. The frequency dependence of the out-of-phase component in alternating current magnetic susceptibilities for both complexes 1 and 2 indicates the slow magnetic relaxation of superparamagnetic behaviour with a Ueff of 27.0(1) K and τ0 = 3.8(2) × 10-9 s for complex 1, and Ueff of 25.1(6) K and τ0 = 4.6(1) × 10-8 s for complex 2.",
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Synthesis, structures and magnetic properties of two hexanuclear complexes. / Yang, Chen I.; Cheng, Kai Hung; Nakano, Motohiro; Lee, Gene Hsiang; Tsai, Hui-Lien.

In: Polyhedron, Vol. 28, No. 9-10, 22.06.2009, p. 1842-1851.

Research output: Contribution to journalArticle

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T1 - Synthesis, structures and magnetic properties of two hexanuclear complexes

AU - Yang, Chen I.

AU - Cheng, Kai Hung

AU - Nakano, Motohiro

AU - Lee, Gene Hsiang

AU - Tsai, Hui-Lien

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N2 - The reaction of salicylaldoxime (H2salox) with Mn(ClO4)2 · 6H2O, NaN(CN)2 and NEt3 in MeOH affords a MnIII6 hexanuclear complex of [Mn6O2(salox)6(MeOH)6(NCNCONH2)2] (1), while reaction of H2salox with MnCl2 · 4H2O and NEt4OH in EtOH affords a MnIII6 hexanuclear complex of [Mn6O2(salox)6(EtOH)4(H2O)2Cl2] (2). Both complexes 1 and 2 contain a [MnIII6(μ3-O)2]14+ core, which is a known structural type in the family of Mn6 complexes. Variable temperature magnetic susceptibilities and magnetization measurement of complexes 1 and 2 have been carried out. Exchange interactions of metal centers for complexes 1 and 2 are fitted by a full diagonalization matrix method. The fitting results indicate that both complexes 1 and 2 have the ground-state spin value of S = 4, and the ground state of complex 1 has the much closer energy to low-lying spin states than that of complex 2. Magnetization measurements at 2.0-4.0 K and 10-70 kG confirm that the ground state is S = 4, with significant magnetoanisotropy as gauged by the D value of -0.82 cm-1 and -1.18 cm-1, for 1 and 2, respectively. The frequency dependence of the out-of-phase component in alternating current magnetic susceptibilities for both complexes 1 and 2 indicates the slow magnetic relaxation of superparamagnetic behaviour with a Ueff of 27.0(1) K and τ0 = 3.8(2) × 10-9 s for complex 1, and Ueff of 25.1(6) K and τ0 = 4.6(1) × 10-8 s for complex 2.

AB - The reaction of salicylaldoxime (H2salox) with Mn(ClO4)2 · 6H2O, NaN(CN)2 and NEt3 in MeOH affords a MnIII6 hexanuclear complex of [Mn6O2(salox)6(MeOH)6(NCNCONH2)2] (1), while reaction of H2salox with MnCl2 · 4H2O and NEt4OH in EtOH affords a MnIII6 hexanuclear complex of [Mn6O2(salox)6(EtOH)4(H2O)2Cl2] (2). Both complexes 1 and 2 contain a [MnIII6(μ3-O)2]14+ core, which is a known structural type in the family of Mn6 complexes. Variable temperature magnetic susceptibilities and magnetization measurement of complexes 1 and 2 have been carried out. Exchange interactions of metal centers for complexes 1 and 2 are fitted by a full diagonalization matrix method. The fitting results indicate that both complexes 1 and 2 have the ground-state spin value of S = 4, and the ground state of complex 1 has the much closer energy to low-lying spin states than that of complex 2. Magnetization measurements at 2.0-4.0 K and 10-70 kG confirm that the ground state is S = 4, with significant magnetoanisotropy as gauged by the D value of -0.82 cm-1 and -1.18 cm-1, for 1 and 2, respectively. The frequency dependence of the out-of-phase component in alternating current magnetic susceptibilities for both complexes 1 and 2 indicates the slow magnetic relaxation of superparamagnetic behaviour with a Ueff of 27.0(1) K and τ0 = 3.8(2) × 10-9 s for complex 1, and Ueff of 25.1(6) K and τ0 = 4.6(1) × 10-8 s for complex 2.

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