Ferromagnetic and antiferromagnetic polymeric complexes with the macrocyclic ligand 1,4,7-triazacyclononane

Ferromagnetic and antiferromagnetic polymeric complexes with the macrocyclic ligand 1,4,7-triazacyclononane
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DOI:
10.1002/ejic.200300791
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发表时间:
2004-06-07
影响因子:
2.3
通讯作者:
Wang, GL
Wang, GL
中科院分区:
化学3区
文献类型:
--
作者:
Cheng, P;Yan, SP;Wang, GL

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三种新型铜聚合物,{[Cu4(Tacn)(4)(o-BDA)(2)]-(ClO4)(4)(H2O)(2)}(N)(1),{[Cu2(Tacn)(m-BDA)](CH3OH)(0,5)(H2O)(0.5)}(N)(2),{[Cu2(Tacn)(2)(p-BDA)](ClO4)(2)(N)(3)(Tacn=1,4,7-三氮杂环烷,BDA=苯二甲酸)的合成和结构表征。化合物1属于单斜晶系C2空间群,而化合物2和3分别属于正交晶系空间群Pmc2(L)和单斜晶系空间群P2(1)/n。它们都是一维锯齿形聚合物,可以认为是由苯二甲酸的异构体连接起来的铜(Tacn)21结构单元。变温(2-300K)磁行为表明,1和2存在铁磁相互作用。实验磁化率的最佳拟合数分别为J=4.0 cm(-1)和g=2.04,J=1.2 cm(-1),ZJ‘=-0.18 cm(-1)和g=2.07(2),而Cu-II离子之间的交换耦合为反铁磁性,J=-13.1 cm(-1)和g=2.05。铜离子之间的相互作用从铁磁性向反铁磁性的转变与苯二甲酸异构体的变化密切相关。(C)Wiley-VCH Verlag GmbH&Co.KGaA,69451,德国温海姆。
Three novel copper polymers, {[Cu-4(tacn)(4)(o-bda)(2)]- (ClO4)(4)(H2O)(2)}(n) (1), {[Cu(tacn)(m-bda)](CH3OH)(0,5)(H2O)(0.5)}(n) (2), and {[Cu-2(tacn)(2)(p-bda)](ClO4)(2)}(n) (3) (tacn = 1,4,7-triazacyclononane, bda = benzenedicarboxylic acid) have been synthesized and structurally characterized. Compound 1 belongs to the monoclinic space group C2, while 2 and 3 crystallize in the orthorhombic space group Pmc2(l) and the monoclinic space group P2(1)/n, respectively. They are all 1D zigzag polymers, which can be considered as Cu(tacn)21 building units linked by isomers of benzenedicarboxylic acid. The variable-temperature (2-300 K) magnetic behavior revealed the existence of ferromagnetic interactions in 1 and 2. The best fittings of the experimental magnetic susceptibilities gave J = 4.0 cm(-1) and g = 2.04 for 1, J = 1.2 cm(-1), zJ' = -0.18 cm(-1) and g = 2.07 for 2, whereas the exchange coupling between Cu-II ions in 3 is antiferromagnetic with J = -13.1 cm(-1) and g = 2.05. The transformation of interactions between copper ions from ferromagnetic to antiferromagnetic is closely related to the variations in the isomeric benzenedicarboxylic acids. (C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004.