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Synthesis,Crystal Structure and Ferromagnetic Properties of a New Dicyanamide Bridged Dicopper(Ⅱ) Complex with IM-1'-MeBzIm-k2 N,O Mode
作者姓名:JIANG Kai  ;CHENG Jiang-Tao  ;WANG Li-Ya  ;WANG Yu-Fang
作者单位:[1]College of Chemistry and Environmental Science,ttenan Normal University, Xinxiang 453002, China; [2]College of Chemistry and Chemical Engineering,Luoyang Normal University, Luoyang 471022, China
基金项目:This work was supported by the National Natural Science Foundation of China (Nos. 20471026 and 20771054) and the Henan Tackle Key Problem of Science and Technology (No. 0524220001)
摘    要:A new dinuclear copper(Ⅱ) complex with imino nitroxide radicals Cu2(NO3)2(IM- 1 ′-MeBzIm)2(dca)2] (IM-1 ′-MeBzIm = 2-{2′-(1′-methyl)benzimidazolyl]}-4,4,5,5-tetramethylimidazoline-1-oxyl, dca = dicyanamide anion) has been prepared and structurally characterized by single-crystal X-ray diffraction. The complex crystallizes in triclinic, space group P 1^-, with α = 9.440(5), b = 10.124(6), c = 11.603(7) A, α = 102.904(7), β = 94.033(6),γ = 104.299(7)°, C34H40Cu2N16O8, Mr = 927.90, V= 1038.2(10) A^3, Z = 1, Dc = 1.484 g/cm^3, μ(MoKα) = 1.093 mm^-1, F(000) = 478, R = 0.0609 and wR = 0.1512 for 2889 observed reflections with Ⅰ 〉 2σ(I). X-ray analysis reveals that two Cu(Ⅱ) atoms are bridged by two dicyanamides to form a centrosymmetric Cu(Ⅱ)-Cu(Ⅱ) dinuclear entity. Every Cu(Ⅱ) ion is five-coordinated with a distorted square pyramidal coordination geometry and IM-1′-MeBzlm ligand coordinates to the metal ion with the k^2 N(1 ′-MeBzlm), O(IM) mode to avoid steric hindrance with the methyl group in the complex. Meanwhile, the molecules are linked by intermolecular hydrogen bonds, leading to a 1-D chain structure. Moreover, such chains are further linked by π-π stacking interactions to form a 2-D network structure. Magnetic measurement demonstrates that the intramolecular exchange couplings between Cu(Ⅱ) ion and the IM-1 ′-MeBzIm are ferromagnetic with J = 12.46 cm^-1, where the spin Hamitonian is defined as H^ = -2JS^1S^2 within the complex.

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