A new class of heterobinuclear complexes: Crystal structure and magnetism of copper(II)-nickel(II) complexes incorporating two different macrocyclic ligands

  • En Qing Gao
  • , Jin Kui Tang
  • , Dai Zheng Liao*
  • , Zong Hui Jiang
  • , Shi Ping Yan
  • , Geng Lin Wang
  • *Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

53 Scopus citations

Abstract

Three novel oxamido-bridged heterobinuclear copper(II)-nickel(II) complexes incorporating two different tetraazamacrocyclic compounds were synthesized and characterized by IR, ESR, and electronic spectra. They are of the formulas [(CuL1)Ni(rac-cth)](ClO)42·H2O (1), [Cu(L2)Ni(rac-cth)](ClO4)2·0.5 EtOH (2), and [(CuL3)Ni(rac-cth)](ClO4)2·H 2O (3). L1, L2, and L3 are the dianions of diethyl 5,6,7,8,16,17-hexahydro-6,7-dioxo-15H-dibenzo[e,n][1,4,8,12] tetraazacyclopentadecine-13,19-decarboxylate, diethyl 5,6,7,8,15,16-hexahydro-6,7-dioxodibenzo[1,4,8,11] tetraazacyclotetracine-13,18-decarboxylate, and diethyl 5,6,7,8,15,16-hexahydro-15-methyl-6,7-dioxodibenzo[1,4,8,11] tetraazacyclotetracine-13,18-decarboxylate, respectively, and rac-cth is rac-5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane. The crystal structures of 1 and 2 were determined by single-crystal X-ray analysis. The NiII ion is pseudooctahedrally coordinated. The coordination geometry around the CuII ion in 2 is slightly distorted square planar, while that in 1 shows significant distortion towards a tetrahedral structure. The temperature dependence of the magnetic susceptibility for 1 and 2 was analyzed by means of the Hamiltonian Ĥ = - 2JŜ1·Ŝ2, leading to J = - 63.9 and -67.4 cm-1 for 1 and 2, respectively.

Original languageEnglish
Pages (from-to)908-917
Number of pages10
JournalHelvetica Chimica Acta
Volume84
Issue number4
DOIs
StatePublished - 2001
Externally publishedYes

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