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Citation: XIE Qi-Wei, CUI Ai-Li, KOU Hui-Zhong. Synthesis, Structure and Magnetic Properties of Phenoxo-Bridged Polynuclear Cu(Ⅱ) Complexes[J]. Chinese Journal of Inorganic Chemistry, ;2015, 31(9): 1798-1804. doi: 10.11862/CJIC.2015.219 shu

Synthesis, Structure and Magnetic Properties of Phenoxo-Bridged Polynuclear Cu(Ⅱ) Complexes

  • 1.

    Department of Chemistry, Tsinghua University, Beijing 100084, China

  • Corresponding author: KOU Hui-Zhong, 
  • Received Date: 7 May 2014
    Available Online: 2 June 2015

    Fund Project: 国家重点基础研究发展计划(No.2013CB933403) (No.2013CB933403)国家自然科学基金(No.91222104,21771103,20121318518)资助项目。 (No.91222104,21771103,20121318518)

  • Two polynuclear copper complexes containing the flexible ligand N, N'-dimethyl-N, N'-(2-hydroxy-4, 5-dimethylbenzyl)ethylenediamine (H2L) have been prepared and characterized structurally and magnetically. The complexes have the formula [Cu3II(L)2(CH3OH)2](ClO4)2(1) and [Cu3II(L)2(CuICl2)2](2). X-ray single-crystal structure analyses show that both complexes contain linear CuII-CuII-CuII cores where adjacent Cu(Ⅱ) ions are doubly bridged by phenolate groups of L2-. The coordination sphere of the terminal Cu(Ⅱ) ions is square pyramidal with the methanol oxygen (complex 1) or the chloride ion of [CuCl2]- (complex 2) situated at the apical position, whereas the central Cu(Ⅱ) has a square coordination environment. The CuII-O-CuII bridging bond angles are in the range of 100.14°~101.79°. Magnetic studies show that both complexes exhibit strong antiferromagnetic interaction with the spin exchange coupling constants (J) of -277(9) cm-1 (1) and -299(3) cm-1 (2) (Ĥ=-2J(Ŝ1·Ŝ2+Ŝ2·Ŝ3). The antiferromagnetic interactions have been found to be mainly related to the CuII-O-CuII bond angles. Larger Cu-O-Cu bond angles correspond to stronger antiferromagnetic interaction (more negative J values).
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