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 [Cu₃^II(L)₂(CH₃OH)₂](ClO₄)₂(1) and [Cu₃^II(L)₂(Cu^ICl₂)₂](2). X-ray single-crystal structure analyses show that both complexes contain linear Cu^II-Cu^II-Cu^II cores where adjacent Cu(Ⅱ) ions are doubly bridged by phenolate groups of L^2-. 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 Cu^II-O-Cu^II 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 Cu^II-O-Cu^II bond angles. Larger Cu-O-Cu bond angles correspond to stronger antiferromagnetic interaction (more negative J values).
- flexible ligand;copper;polynuclear;magnetism;mixed-valent
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沈阳化工大学材料科学与工程学院沈阳 110142