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Preparation, characterization and crystal structures of copper(II) hexaazamacrotetracyclic complexes with organic ligands


The reaction of [Cu(L)](ClO4)2 · H2O (L=1,3,10,12,16,19-hexaazatetracyclo[17,3,1,112.16,04.9]tetracosane) with NaN3 and Na2tp yields mononuclear and dinuclear copper(II) complexes, [Cu(L)(N3)](ClO4) (1) and [Cu(L)(μ-tp)](ClO4) · 2H2O (2). These complexes have been characterized by X-ray crystallography, electronic absorption, cyclic voltammetry and magnetic susceptibility. The crystal structure of (1) shows that the copper(II) ion has a distorted square-pyramidal geometry with the two secondary and two tertiary amines of the macrocycle and one nitrogen atom from the azide group coordinating the axial position. The copper(II) ions in (2) are bridged by the terephthalate anion to form a dinuclear complex, in which each copper(II) ion reveals a distorted square-pyramid with four nitrogen atoms of the macrocycle and the oxygen atom of bridging tp ligand. Cyclic voltammetry of the complexes gives two one-electron waves corresponding to CuII/CuIII and CuII/CuI processes. The magnetic susceptibility measurement for (2) exhibits a weak antiferromagnetic interaction between copper(II) centers with a 2J value of −2.21 cm−1 (H = −2JΣS1 · S2). The electronic spectra and electrochemical behavior of the complexes are significantly affected by the nature of the organic ligands.

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Correspondence to Ki-Young Choi.

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Choi, K., Kim, M. & Kim, M. Preparation, characterization and crystal structures of copper(II) hexaazamacrotetracyclic complexes with organic ligands. Transition Met Chem 29, 904–910 (2004).

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  • Nitrogen Atom
  • Magnetic Susceptibility
  • Cyclic Voltammetry
  • Terephthalate
  • Macrocycle