Trinuclear CuIIMIICuII complexes of an oxamide/dioxime ligand and extension to a bimetallic magnetic compound

Nobuo Fukita, Masaaki Ohba, Takuya Shiga, Hisashi Okawa, Yoshitami Ajiro

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Abstract

N,N′-Bis[2-(hydroxyiminomethyl)phenyl]oxamide (H4L) provided trinuclear CuIIMIICuII complexes [M{Cu(HL)-(DMF)}2(DMF)2] (MII = Mn 1, Co 2, Ni 3 or Zn 4). The crystal structures of 1-4 have been determined by X-ray crystallography. They are isomorphous and have an oxamidate-bridged trinuclear CuIIMIICuII structure. The CuII resides in a pseudo-macrocyclic framework of (HL)3- comprised of an oxamidate and a hydrogen-bonded dioximate (=N-O⋯H⋯O-N=) groups to form a square-pyramidal structure {Cu(HL)(DMF)} together with a DMF molecule. Two {Cu(HL)(DMF)} entities co-ordinate to a MnII through the oxamidate oxygens to afford a cis octahedral environment about the metal together with two DMF oxygens. The CuII⋯MII intermetallic distance separated by the oxamidate bridge is 5.33-5.49 Å. In the case of 1 and 3 a significant antiferromagnetic interaction operates between the adjacent CuII and MII. The reaction of 1 with MnII in acetonitrile in the presence of KOH and 18-crown-6 formed Mn{Cu(L)}(H2O)4 that has a polymeric structure extended by the dioximate-MnII-dioximate linkage. It is a weak ferromagnet (TC = 5.5 K) exhibiting a weak antiferromagnetic interaction between the ferrimagnetic chains.

Original languageEnglish
Pages (from-to)64-70
Number of pages7
JournalJournal of the Chemical Society, Dalton Transactions
Issue number1
DOIs
Publication statusPublished - Dec 1 2001

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Oxygen
Ligands
X ray crystallography
Intermetallics
Hydrogen
Crystal structure
Metals
Molecules
oxamide
acetonitrile
18-crown-6

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

Cite this

Trinuclear CuIIMIICuII complexes of an oxamide/dioxime ligand and extension to a bimetallic magnetic compound. / Fukita, Nobuo; Ohba, Masaaki; Shiga, Takuya; Okawa, Hisashi; Ajiro, Yoshitami.

In: Journal of the Chemical Society, Dalton Transactions, No. 1, 01.12.2001, p. 64-70.

Research output: Contribution to journalArticle

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abstract = "N,N′-Bis[2-(hydroxyiminomethyl)phenyl]oxamide (H4L) provided trinuclear CuIIMIICuII complexes [M{Cu(HL)-(DMF)}2(DMF)2] (MII = Mn 1, Co 2, Ni 3 or Zn 4). The crystal structures of 1-4 have been determined by X-ray crystallography. They are isomorphous and have an oxamidate-bridged trinuclear CuIIMIICuII structure. The CuII resides in a pseudo-macrocyclic framework of (HL)3- comprised of an oxamidate and a hydrogen-bonded dioximate (=N-O⋯H⋯O-N=) groups to form a square-pyramidal structure {Cu(HL)(DMF)} together with a DMF molecule. Two {Cu(HL)(DMF)} entities co-ordinate to a MnII through the oxamidate oxygens to afford a cis octahedral environment about the metal together with two DMF oxygens. The CuII⋯MII intermetallic distance separated by the oxamidate bridge is 5.33-5.49 {\AA}. In the case of 1 and 3 a significant antiferromagnetic interaction operates between the adjacent CuII and MII. The reaction of 1 with MnII in acetonitrile in the presence of KOH and 18-crown-6 formed Mn{Cu(L)}(H2O)4 that has a polymeric structure extended by the dioximate-MnII-dioximate linkage. It is a weak ferromagnet (TC = 5.5 K) exhibiting a weak antiferromagnetic interaction between the ferrimagnetic chains.",
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