Crystal structures and magnetic behaviors of cyanido-bridged dinuclear dimetallic systems involving 3d-3d or 3d-5d metal centers

Il Kim Jae, Hee Yoon Jung, Young Kwak Hyun, Kwan Koh Eui, Chang Seop Hong

Research output: Contribution to journalArticle

1 Citation (Scopus)

Abstract

Three cyanido-bridged FeIII-MnII dimers, [Fe(pzcq)(CN)3]-[Mn(phen)2(X)]·MeOH [X = Cl (1), Br (2); pzcq = 8-(pyrazine-2-carboxamido)quinoline anion, phen = 1,10-phenanthroline], [Fe(mpzcq)(CN)3][Mn(phen)2(Cl)] ·MeOH [3; mpzcq = 8-(5-methylpyrazine-2-carboxamido)quinoline anion], and one WV-MnII dinuclear system, [W(bpy)(CN) 6][Mn(phen)2(Cl)]·MeOH (4; bpy = 2,2′-bipyridine), were prepared by assembling molecular precursors, [Fe(pzcq)(CN)3]-, [Fe(mpzcq)-(CN)3] -, and [W(bpy)(CN)6]-, with Mn(phen) 2X2. The absolute configurations of the Mn polyhedra surrounded by two bidentate phen ligands are packed in a -Δ-Λ- Δ-Λ- sequence in the crystal lattice. The aromatic rings of the coordinated phen ligands are sources of considerable interdimer π-π contacts, which eventually lead to the formation of two-dimensional frameworks (1-3) and a one-dimensional chain structure (4). Magnetic analyses of the FeIII-MnII dinuclear systems (1-3) reveal that a shorter Mn-N(cyanide) bond and a more linear Mn-N-C(cyanide) angle allow for stronger magnetic exchange coupling. Moreover, it is manifested that the 3d-5d magnetic coupling in 4 is stronger than the 3d-3d coupling in 1-3 under the given structural environments, which is due to the fact that the 5d orbital is more diffuse than the 3d orbital.

Original languageEnglish
Pages (from-to)2756-2763
Number of pages8
JournalEuropean Journal of Inorganic Chemistry
Issue number17
DOIs
Publication statusPublished - 2008 Jun 1

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Cyanides
Anions
Crystal structure
Metals
Ligands
Pyrazines
Magnetic couplings
Exchange coupling
Crystal lattices
Dimers
quinoline
1,10-phenanthroline

Keywords

  • Crystal structure
  • Cyanides
  • Dinuclear complexes
  • Magnetism
  • N ligands

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Crystal structures and magnetic behaviors of cyanido-bridged dinuclear dimetallic systems involving 3d-3d or 3d-5d metal centers. / Jae, Il Kim; Jung, Hee Yoon; Hyun, Young Kwak; Eui, Kwan Koh; Hong, Chang Seop.

In: European Journal of Inorganic Chemistry, No. 17, 01.06.2008, p. 2756-2763.

Research output: Contribution to journalArticle

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abstract = "Three cyanido-bridged FeIII-MnII dimers, [Fe(pzcq)(CN)3]-[Mn(phen)2(X)]·MeOH [X = Cl (1), Br (2); pzcq = 8-(pyrazine-2-carboxamido)quinoline anion, phen = 1,10-phenanthroline], [Fe(mpzcq)(CN)3][Mn(phen)2(Cl)] ·MeOH [3; mpzcq = 8-(5-methylpyrazine-2-carboxamido)quinoline anion], and one WV-MnII dinuclear system, [W(bpy)(CN) 6][Mn(phen)2(Cl)]·MeOH (4; bpy = 2,2′-bipyridine), were prepared by assembling molecular precursors, [Fe(pzcq)(CN)3]-, [Fe(mpzcq)-(CN)3] -, and [W(bpy)(CN)6]-, with Mn(phen) 2X2. The absolute configurations of the Mn polyhedra surrounded by two bidentate phen ligands are packed in a -Δ-Λ- Δ-Λ- sequence in the crystal lattice. The aromatic rings of the coordinated phen ligands are sources of considerable interdimer π-π contacts, which eventually lead to the formation of two-dimensional frameworks (1-3) and a one-dimensional chain structure (4). Magnetic analyses of the FeIII-MnII dinuclear systems (1-3) reveal that a shorter Mn-N(cyanide) bond and a more linear Mn-N-C(cyanide) angle allow for stronger magnetic exchange coupling. Moreover, it is manifested that the 3d-5d magnetic coupling in 4 is stronger than the 3d-3d coupling in 1-3 under the given structural environments, which is due to the fact that the 5d orbital is more diffuse than the 3d orbital.",
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AB - Three cyanido-bridged FeIII-MnII dimers, [Fe(pzcq)(CN)3]-[Mn(phen)2(X)]·MeOH [X = Cl (1), Br (2); pzcq = 8-(pyrazine-2-carboxamido)quinoline anion, phen = 1,10-phenanthroline], [Fe(mpzcq)(CN)3][Mn(phen)2(Cl)] ·MeOH [3; mpzcq = 8-(5-methylpyrazine-2-carboxamido)quinoline anion], and one WV-MnII dinuclear system, [W(bpy)(CN) 6][Mn(phen)2(Cl)]·MeOH (4; bpy = 2,2′-bipyridine), were prepared by assembling molecular precursors, [Fe(pzcq)(CN)3]-, [Fe(mpzcq)-(CN)3] -, and [W(bpy)(CN)6]-, with Mn(phen) 2X2. The absolute configurations of the Mn polyhedra surrounded by two bidentate phen ligands are packed in a -Δ-Λ- Δ-Λ- sequence in the crystal lattice. The aromatic rings of the coordinated phen ligands are sources of considerable interdimer π-π contacts, which eventually lead to the formation of two-dimensional frameworks (1-3) and a one-dimensional chain structure (4). Magnetic analyses of the FeIII-MnII dinuclear systems (1-3) reveal that a shorter Mn-N(cyanide) bond and a more linear Mn-N-C(cyanide) angle allow for stronger magnetic exchange coupling. Moreover, it is manifested that the 3d-5d magnetic coupling in 4 is stronger than the 3d-3d coupling in 1-3 under the given structural environments, which is due to the fact that the 5d orbital is more diffuse than the 3d orbital.

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