Two WV–MnIII bimetallic assemblies built by octacyanotungstate(v) and MnIII Schiff bases

Molecular structures and a spin-flop transition

Hyun Hee Ko, Jeong Hak Lim, Houng Sik Yoo, Jun Sung Kang, Hyoung Chan Kim, Eui Kwan Koh, Chang Seop Hong

Research output: Contribution to journalArticle

21 Citations (Scopus)

Abstract

Two WV–MnIII bimetallic compounds, [Mn(Cl-salmen)(H2O)2]([Mn(5-Clsalmen)(H2O)]2[W(CN)8]·2H2O (1·2H2O) [5-Clsalmen = N, N′-(1-methylethylene)bis(5-chlorosalicylideneiminato) dianion], which contains trinuclear Mn2W and isolated MnIII moieties, and [Mn(3-MeOsalcy)(H2O)2]3[W(CN)8]·2H2O (2·2H2O) [3-MeOsalcy = N, N′-(trans-1,2-cyclohexanediylethylene)bis(3-methoxysalicylideneiminato) dianion] molecules were prepared in redox processes and characterized using X-ray analysis and magnetic measurements. Compound 1 is composed of the ([Mn(5-Clsalmen)(H2O)]2[W(CN)8]) trimer, in which two CN groups among eight in [W(CN)8]3− bridge W5+ and two Mn3+ ions and the remaining CN ligands are hydrogen-bonded to water molecules or unbound, and the [Mn(Cl-salmen)(H2O)2]+ cation. Subsequently, two water molecules of the isolated cation are subject to hydrogen bonds. For 2, there are no covalent bonds among the subunits and six serial stacks of [Mn(3-MeOsalcy)(H2O)2]+ units are all hydrogen-bonded. The many hydrogen bonds found in both complexes eventually lead to three-dimensional networks. The magnetic studies for 1 reveal that antiferromagnetic interactions (J = −5.4 cm−1) between WV and MnIII centers within the trimer are transmitted via the bridging CN groups. Intermolecular antiferromagnetic couplings (zJ′ = −0.2 cm−1) are also observed. The static and dynamic magnetic data of 1 demonstrate the existence of a field-induced spin-flop transition occurring among the clusters and monomeric molecules.

Original languageEnglish
Pages (from-to)2070-2076
Number of pages7
JournalJournal of the Chemical Society. Dalton Transactions
Issue number20
DOIs
Publication statusPublished - 2007 Mar 30

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Schiff Bases
Molecular structure
Molecules
Cations
Hydrogen
Hydrogen bonds
Covalent bonds
Water
X ray analysis
Magnetic variables measurement
Ions
Ligands

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Two WV–MnIII bimetallic assemblies built by octacyanotungstate(v) and MnIII Schiff bases : Molecular structures and a spin-flop transition. / Ko, Hyun Hee; Lim, Jeong Hak; Yoo, Houng Sik; Kang, Jun Sung; Kim, Hyoung Chan; Koh, Eui Kwan; Hong, Chang Seop.

In: Journal of the Chemical Society. Dalton Transactions, No. 20, 30.03.2007, p. 2070-2076.

Research output: Contribution to journalArticle

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abstract = "Two WV–MnIII bimetallic compounds, [Mn(Cl-salmen)(H2O)2]([Mn(5-Clsalmen)(H2O)]2[W(CN)8]·2H2O (1·2H2O) [5-Clsalmen = N, N′-(1-methylethylene)bis(5-chlorosalicylideneiminato) dianion], which contains trinuclear Mn2W and isolated MnIII moieties, and [Mn(3-MeOsalcy)(H2O)2]3[W(CN)8]·2H2O (2·2H2O) [3-MeOsalcy = N, N′-(trans-1,2-cyclohexanediylethylene)bis(3-methoxysalicylideneiminato) dianion] molecules were prepared in redox processes and characterized using X-ray analysis and magnetic measurements. Compound 1 is composed of the ([Mn(5-Clsalmen)(H2O)]2[W(CN)8])− trimer, in which two CN groups among eight in [W(CN)8]3− bridge W5+ and two Mn3+ ions and the remaining CN ligands are hydrogen-bonded to water molecules or unbound, and the [Mn(Cl-salmen)(H2O)2]+ cation. Subsequently, two water molecules of the isolated cation are subject to hydrogen bonds. For 2, there are no covalent bonds among the subunits and six serial stacks of [Mn(3-MeOsalcy)(H2O)2]+ units are all hydrogen-bonded. The many hydrogen bonds found in both complexes eventually lead to three-dimensional networks. The magnetic studies for 1 reveal that antiferromagnetic interactions (J = −5.4 cm−1) between WV and MnIII centers within the trimer are transmitted via the bridging CN groups. Intermolecular antiferromagnetic couplings (zJ′ = −0.2 cm−1) are also observed. The static and dynamic magnetic data of 1 demonstrate the existence of a field-induced spin-flop transition occurring among the clusters and monomeric molecules.",
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AU - Ko, Hyun Hee

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AU - Yoo, Houng Sik

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AU - Koh, Eui Kwan

AU - Hong, Chang Seop

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