Synthesis and Characterization of a Di-µ-oxalato Tetracopper(II) Complex with Tetranucleating Macrocyclic Ligand

A tetracopper(II) complex containing two oxalate anions in the metal-based host cavity, [Cu4(Lpy)(µ-ox)2](PF6)2·2(2-PrOH), where ox2−: oxalato (C2O42−), was prepared by reacting H2Lpy, a phenol-based tetranucleating macrocyclic ligand with four pyridylmethyl pendant arms, Cu(ClO4)2·6H2O, and sodium...

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Published inBulletin of the Chemical Society of Japan Vol. 89; no. 4; pp. 430 - 436
Main Authors Miyazato, Yuji, Asato, Eiji, Ohba, Masaaki, Wada, Tohru
Format Journal Article
LanguageEnglish
Published TOKYO The Chemical Society of Japan 15.04.2016
Chemical Soc Japan
Chemical Society of Japan
Subjects
Anion exchanging
Antiferromagnetism
Chemistry
Chemistry, Multidisciplinary
Diffraction
Holes
Ligands
Macrocyclic compounds
Methyl alcohol
Oxalates
Physical Sciences
Science & Technology
Sodium
COORDINATION CHEMISTRY
BRIDGED COPPER(II)
SERIES
ARRANGEMENT
RAY CRYSTAL-STRUCTURES
IONS
MAGNETIC-PROPERTIES
ZINC(II)
1,4,7-TRIAZACYCLONONANE
NICKEL(II)
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Abstract A tetracopper(II) complex containing two oxalate anions in the metal-based host cavity, [Cu4(Lpy)(µ-ox)2](PF6)2·2(2-PrOH), where ox2−: oxalato (C2O42−), was prepared by reacting H2Lpy, a phenol-based tetranucleating macrocyclic ligand with four pyridylmethyl pendant arms, Cu(ClO4)2·6H2O, and sodium oxalate (1:4:2 stoichiometry, respectively) in methanol, followed by exchange of the counteranion with excess of NH4PF6. Single-crystal X-ray diffraction of 1 revealed that two {Cu(II)Cu(II)} units, bridged by a phenolato group of Lpy2−, were connected by two oxalato anions, to construct a rectangular “{CuCu}(µ-ox)2{CuCu}” tetranuclear framework. This rectangular framework was maintained in DMF solution. The magnetic measurement of 1 in the 2–300 K range revealed antiferromagnetic behavior. The antiferromagnetic interaction in this complex occurs between the Cu(II) centers bridged by an oxalate (J = −140 cm−1).
AbstractList A tetracopper(II) complex containing two oxalate anions in the metal-based host cavity, [Cu4(Lpy)(µ-ox)2](PF6)2·2(2-PrOH), where ox2-: oxalato (C2O42-), was prepared by reacting H2Lpy, a phenol-based tetranucleating macrocyclic ligand with four pyridylmethyl pendant arms, Cu(ClO4)2·6H2O, and sodium oxalate (1:4:2 stoichiometry, respectively) in methanol, followed by exchange of the counteranion with excess of NH4PF6. Single-crystal X-ray diffraction of 1 revealed that two {Cu(II)Cu(II)} units, bridged by a phenolato group of Lpy2-, were connected by two oxalato anions, to construct a rectangular "{CuCu}(µ-ox)2{CuCu}" tetranuclear framework. This rectangular framework was maintained in DMF solution. The magnetic measurement of 1 in the 2-300 K range revealed antiferromagnetic behavior. The antiferromagnetic interaction in this complex occurs between the Cu(II) centers bridged by an oxalate (J = -140 cm-1).
A tetracopper(II) complex containing two oxalate anions in the metal-based host cavity, [Cu4(Lpy)(µ-ox)2](PF6)2·2(2-PrOH), where ox2−: oxalato (C2O42−), was prepared by reacting H2Lpy, a phenol-based tetranucleating macrocyclic ligand with four pyridylmethyl pendant arms, Cu(ClO4)2·6H2O, and sodium oxalate (1:4:2 stoichiometry, respectively) in methanol, followed by exchange of the counteranion with excess of NH4PF6. Single-crystal X-ray diffraction of 1 revealed that two {Cu(II)Cu(II)} units, bridged by a phenolato group of Lpy2−, were connected by two oxalato anions, to construct a rectangular “{CuCu}(µ-ox)2{CuCu}” tetranuclear framework. This rectangular framework was maintained in DMF solution. The magnetic measurement of 1 in the 2–300 K range revealed antiferromagnetic behavior. The antiferromagnetic interaction in this complex occurs between the Cu(II) centers bridged by an oxalate (J = −140 cm−1).
A tetracopper(II) complex containing two oxalate anions in the metal-based host cavity, [Cu4(Lpy)( mu -ox)2](PF6)2.2(2-PrOH), where ox2-: oxalato (C2O42-), was prepared by reacting H2Lpy, a phenol-based tetranucleating macrocyclic ligand with four pyridylmethyl pendant arms, Cu(ClO4)2.6H2O, and sodium oxalate (1:4:2 stoichiometry, respectively) in methanol, followed by exchange of the counteranion with excess of NH4PF6. Single-crystal X-ray diffraction of 1 revealed that two {Cu(II)Cu(II)} units, bridged by a phenolato group of Lpy2-, were connected by two oxalato anions, to construct a rectangular "{CuCu}( mu -ox)2{CuCu}" tetranuclear framework. This rectangular framework was maintained in DMF solution. The magnetic measurement of 1 in the 2-300 K range revealed antiferromagnetic behavior. The antiferromagnetic interaction in this complex occurs between the Cu(II) centers bridged by an oxalate (J = -140 cm-1).
Abstract A tetracopper(II) complex containing two oxalate anions in the metal-based host cavity, [Cu4(Lpy)(µ-ox)2](PF6)2·2(2-PrOH), where ox2−: oxalato (C2O42−), was prepared by reacting H2Lpy, a phenol-based tetranucleating macrocyclic ligand with four pyridylmethyl pendant arms, Cu(ClO4)2·6H2O, and sodium oxalate (1:4:2 stoichiometry, respectively) in methanol, followed by exchange of the counteranion with excess of NH4PF6. Single-crystal X-ray diffraction of 1 revealed that two {Cu(II)Cu(II)} units, bridged by a phenolato group of Lpy2−, were connected by two oxalato anions, to construct a rectangular “{CuCu}(µ-ox)2{CuCu}” tetranuclear framework. This rectangular framework was maintained in DMF solution. The magnetic measurement of 1 in the 2–300 K range revealed antiferromagnetic behavior. The antiferromagnetic interaction in this complex occurs between the Cu(II) centers bridged by an oxalate (J = −140 cm−1).
A tetracopper(II) complex containing two oxalate anions in the metal-based host cavity, [Cu-4(L-py)(mu-ox)(2)](PF6)(2)center dot 2(2-PrOH), where ox(2-): oxalato (C2O42-), was prepared by reacting H2Lpy, a phenol-based tetranucleating macrocyclic ligand with four pyridylmethyl pendant arms, Cu(ClO4)(2)center dot 6H(2)O, and sodium oxalate (1:4:2 stoichiometry, respectively) in methanol, followed by exchange of the counteranion with excess of NH4PF6. Single-crystal X-ray diffraction of 1 revealed that two {Cu(II)Cu(II)} units, bridged by a phenolato group of L-py(2-), were connected by two oxalato anions, to construct a rectangular "{CuCu}(mu-ox)(2){CuCu}" tetranuclear framework. This rectangular framework was maintained in DMF solution. The magnetic measurement of 1 in the 2-300 K range revealed antiferromagnetic behavior. The antiferromagnetic interaction in this complex occurs between the Cu(II) centers bridged by an oxalate (J = -140 cm(-1)).
Author Ohba, Masaaki
Asato, Eiji
Miyazato, Yuji
Wada, Tohru
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Keywords COORDINATION CHEMISTRY
BRIDGED COPPER(II)
SERIES
ARRANGEMENT
RAY CRYSTAL-STRUCTURES
IONS
MAGNETIC-PROPERTIES
ZINC(II)
1,4,7-TRIAZACYCLONONANE
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Snippet A tetracopper(II) complex containing two oxalate anions in the metal-based host cavity, [Cu4(Lpy)(µ-ox)2](PF6)2·2(2-PrOH), where ox2−: oxalato (C2O42−), was...
A tetracopper(II) complex containing two oxalate anions in the metal-based host cavity, [Cu-4(L-py)(mu-ox)(2)](PF6)(2)center dot 2(2-PrOH), where ox(2-):...
Abstract A tetracopper(II) complex containing two oxalate anions in the metal-based host cavity, [Cu4(Lpy)(µ-ox)2](PF6)2·2(2-PrOH), where ox2−: oxalato...
A tetracopper(II) complex containing two oxalate anions in the metal-based host cavity, [Cu4(Lpy)(µ-ox)2](PF6)2·2(2-PrOH), where ox2-: oxalato (C2O42-), was...
A tetracopper(II) complex containing two oxalate anions in the metal-based host cavity, [Cu4(Lpy)( mu -ox)2](PF6)2.2(2-PrOH), where ox2-: oxalato (C2O42-), was...
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SubjectTerms Anion exchanging
Antiferromagnetism
Chemistry
Chemistry, Multidisciplinary
Diffraction
Holes
Ligands
Macrocyclic compounds
Methyl alcohol
Oxalates
Physical Sciences
Science & Technology
Sodium
Title Synthesis and Characterization of a Di-µ-oxalato Tetracopper(II) Complex with Tetranucleating Macrocyclic Ligand
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