Face-sharing heterotrinuclear MII-LnIII-M II (M = Mn, Fe, Co, Zn; Ln = La, Gd, Tb, Dy) complexes

Synthesis, structures, and magnetic properties

Tomoka Yamaguchi, Jean Pierre Costes, Yukana Kishima, Masaaki Kojima, Yukinari Sunatsuki, Nicolas Bréfuel, Jean Pierre Tuchagues, Laure Vendier, Wolfgang Wernsdorfer

Research output: Contribution to journalArticle

153 Citations (Scopus)

Abstract

Trinuclear linear 3d-4f-3d complexes (3d = MnII, Fe II, CoII, ZnII and 4f = LaIII, GdIII, TbIII, DyIII) were prepared by using a tripodal nonadentate Schiff base ligand, N,N',N"-tris(2-hydroxy-3- methoxybenzilidene)-2-(aminomethyl)-2-methyl-1,3-propanediamine. The structural determinations showed that in these complexes two distorted trigonal prismatic transition metal complexes of identical chirality are assembled through 4f cations. The Mn and Fe entities crystallize in the chiral space group P2 12121 as pure enantiomers; the cobalt complexes exhibit a less straightforward behavior. All Mn, Fe, and Co complexes experience MII-LnIII ferromagnetic interactions. The Mn-Gd interaction is weak (0.08 cm-1) in comparison to the Fe-Gd (0.69 cm-1) and Co-Gd (0.52 cm-1) ones while the single ion zero field splitting (ZFS) term D is larger for the Fe complexes (5.7 cm -1) than for the cobalt ones. The cobalt complexes behave as single-molecules magnets (SMMs) with large magnetization hysteresis loops, as a consequence of the particularly slow magnetic relaxation characterizing these trinuclear molecules. Such large hysteresis loops, which are observed for the first time in Co-Ln complexes, confirm that quantum tunnelling of the magnetization does not operate in the Co-Gd-Co complex.

Original languageEnglish
Pages (from-to)9125-9135
Number of pages11
JournalInorganic Chemistry
Volume49
Issue number20
DOIs
Publication statusPublished - Oct 18 2010

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Cobalt
Magnetic properties
cobalt
Hysteresis loops
magnetic properties
Magnetization
synthesis
hysteresis
Magnetic relaxation
magnetization
Molecules
Enantiomers
Schiff Bases
Chirality
Coordination Complexes
enantiomers
magnetic relaxation
chirality
imines
Transition metals

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry

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Face-sharing heterotrinuclear MII-LnIII-M II (M = Mn, Fe, Co, Zn; Ln = La, Gd, Tb, Dy) complexes : Synthesis, structures, and magnetic properties. / Yamaguchi, Tomoka; Costes, Jean Pierre; Kishima, Yukana; Kojima, Masaaki; Sunatsuki, Yukinari; Bréfuel, Nicolas; Tuchagues, Jean Pierre; Vendier, Laure; Wernsdorfer, Wolfgang.

In: Inorganic Chemistry, Vol. 49, No. 20, 18.10.2010, p. 9125-9135.

Research output: Contribution to journalArticle

Yamaguchi, T, Costes, JP, Kishima, Y, Kojima, M, Sunatsuki, Y, Bréfuel, N, Tuchagues, JP, Vendier, L & Wernsdorfer, W 2010, 'Face-sharing heterotrinuclear MII-LnIII-M II (M = Mn, Fe, Co, Zn; Ln = La, Gd, Tb, Dy) complexes: Synthesis, structures, and magnetic properties', Inorganic Chemistry, vol. 49, no. 20, pp. 9125-9135. https://doi.org/10.1021/ic100460w
Yamaguchi, Tomoka ; Costes, Jean Pierre ; Kishima, Yukana ; Kojima, Masaaki ; Sunatsuki, Yukinari ; Bréfuel, Nicolas ; Tuchagues, Jean Pierre ; Vendier, Laure ; Wernsdorfer, Wolfgang. / Face-sharing heterotrinuclear MII-LnIII-M II (M = Mn, Fe, Co, Zn; Ln = La, Gd, Tb, Dy) complexes : Synthesis, structures, and magnetic properties. In: Inorganic Chemistry. 2010 ; Vol. 49, No. 20. pp. 9125-9135.
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T1 - Face-sharing heterotrinuclear MII-LnIII-M II (M = Mn, Fe, Co, Zn; Ln = La, Gd, Tb, Dy) complexes

T2 - Synthesis, structures, and magnetic properties

AU - Yamaguchi, Tomoka

AU - Costes, Jean Pierre

AU - Kishima, Yukana

AU - Kojima, Masaaki

AU - Sunatsuki, Yukinari

AU - Bréfuel, Nicolas

AU - Tuchagues, Jean Pierre

AU - Vendier, Laure

AU - Wernsdorfer, Wolfgang

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Y1 - 2010/10/18

N2 - Trinuclear linear 3d-4f-3d complexes (3d = MnII, Fe II, CoII, ZnII and 4f = LaIII, GdIII, TbIII, DyIII) were prepared by using a tripodal nonadentate Schiff base ligand, N,N',N"-tris(2-hydroxy-3- methoxybenzilidene)-2-(aminomethyl)-2-methyl-1,3-propanediamine. The structural determinations showed that in these complexes two distorted trigonal prismatic transition metal complexes of identical chirality are assembled through 4f cations. The Mn and Fe entities crystallize in the chiral space group P2 12121 as pure enantiomers; the cobalt complexes exhibit a less straightforward behavior. All Mn, Fe, and Co complexes experience MII-LnIII ferromagnetic interactions. The Mn-Gd interaction is weak (0.08 cm-1) in comparison to the Fe-Gd (0.69 cm-1) and Co-Gd (0.52 cm-1) ones while the single ion zero field splitting (ZFS) term D is larger for the Fe complexes (5.7 cm -1) than for the cobalt ones. The cobalt complexes behave as single-molecules magnets (SMMs) with large magnetization hysteresis loops, as a consequence of the particularly slow magnetic relaxation characterizing these trinuclear molecules. Such large hysteresis loops, which are observed for the first time in Co-Ln complexes, confirm that quantum tunnelling of the magnetization does not operate in the Co-Gd-Co complex.

AB - Trinuclear linear 3d-4f-3d complexes (3d = MnII, Fe II, CoII, ZnII and 4f = LaIII, GdIII, TbIII, DyIII) were prepared by using a tripodal nonadentate Schiff base ligand, N,N',N"-tris(2-hydroxy-3- methoxybenzilidene)-2-(aminomethyl)-2-methyl-1,3-propanediamine. The structural determinations showed that in these complexes two distorted trigonal prismatic transition metal complexes of identical chirality are assembled through 4f cations. The Mn and Fe entities crystallize in the chiral space group P2 12121 as pure enantiomers; the cobalt complexes exhibit a less straightforward behavior. All Mn, Fe, and Co complexes experience MII-LnIII ferromagnetic interactions. The Mn-Gd interaction is weak (0.08 cm-1) in comparison to the Fe-Gd (0.69 cm-1) and Co-Gd (0.52 cm-1) ones while the single ion zero field splitting (ZFS) term D is larger for the Fe complexes (5.7 cm -1) than for the cobalt ones. The cobalt complexes behave as single-molecules magnets (SMMs) with large magnetization hysteresis loops, as a consequence of the particularly slow magnetic relaxation characterizing these trinuclear molecules. Such large hysteresis loops, which are observed for the first time in Co-Ln complexes, confirm that quantum tunnelling of the magnetization does not operate in the Co-Gd-Co complex.

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