Crystal structure, spectroscopy and magnetism of trinuclear nickel(II), cobalt(II) complexes and their solid solution

Crystal structure, spectroscopy and magnetism of trinuclear nickel(II), cobalt(II) complexes and their solid solution
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三核镍(II)、钴(II)配合物及其固溶体的晶体结构、光谱和磁性

DOI:
10.1016/j.poly.2011.03.024
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发表时间:
2011-11
期刊:
影响因子:
2.6
通讯作者:
Liao, Dai-Zheng
Liao, Dai-Zheng
中科院分区:
化学3区
文献类型:
--
作者:
Tong, Yu-Zhang;Wang, Qing-Lun;Si, Meng;Qi, Jing;Yan, Shi-Ping;Yang, Guang-Ming;Cheng, Peng;Liao, Dai-Zheng

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四个新的配合物[Ni_3(μ-L)_6(H_2O)_6](NO_3)_6·6H_2O(1),[Co_3(μ-L)_6(H_2O)_6](NO_3)_6·6H_2O(2),[Ni_3(μ-L)_6(H_2O)_4(CH_3OH)_2](NO_3)_6·4H_2O(3),[Co_3(μ-L)_6(H_2O)_4(CH_3OH)_2](NO_3)_6·4H_2O(4)(L=4-氨基-3,5-二甲甲基-1,2,4-三唑)的合成,并通过X-射线单晶衍射对其结构进行了表征。结构分析表明,配合物1和2是类质同象的,配合物3和4是类质同象的。四个配合物均由线性三核阳离子(1和2为[M3(μ-L)6(H2O)6]6+(M=Ni,Co); 3和4为[M3(μ-L)6(H2O)4(CH 3OH)2]6+(M=Ni,Co))、NO3−阴离子和结晶水分子组成。在三核阳离子中,中心M(II)离子和两个末端M(II)离子通过三个三唑配体桥接。用不同比例的Ni(II)和Co(II)离子作为反应物,得到了与配合物3和4同晶的11种固溶体化合物,ICP结果表明配体L对Ni(II)离子的选择性高于Co(II)离子。磁性分析是通过使用各向同性自旋哈密顿量ε =− 2 J(国1国2+国2国3)(对于配合物1和3)并同时考虑温度依赖性g因子(对于配合物2和4)来进行的。通过调节Co(II)/Ni(II)的比例,可以系统地改变固溶体的紫外-可见光谱和磁性。
Four new complexes [Ni3(μ-L)6(H2O)6](NO3)6·6H2O (1), [Co3(μ-L)6(H2O)6](NO3)6·6H2O (2), [Ni3(μ-L)6(H2O)4(CH3OH)2](NO3)6·4H2O (3), [Co3(μ-L)6(H2O)4(CH3OH)2](NO3)6·4H2O (4) (L=4-amino-3,5-dimethanyl-1,2,4-triazole) were synthesized and structurally characterized by X-ray single-crystal diffraction. The structural analyses show that complex 1 and 2 are isomorphous; complex 3 and 4 are isomorphous. Four complexes all consist of the linear trinuclear cations ([M3(μ-L)6(H2O)6]6+(M=Ni,Co) for 1 and 2; [M3(μ-L)6(H2O)4(CH3OH)2]6+(M=Ni,Co) for 3 and 4), NO3−anions and crystallized water molecules. In the trinuclear cations, the central M(II) ions and two terminal M(II) ions are bridged by three triazole ligands. Other eleven solid solution compounds which are isomorphous with complex 3 and 4 were obtained by using different ratio of Ni(II) and Co(II) ions as reactants and ICP result indicates that ligand L has higher selectivity of Ni(II) ions than that of Co(II) ions. The magnetic analysis was carried out by using the isotropic spin Hamiltonian Ĥ=−2J(Ŝ1Ŝ2+Ŝ2Ŝ3) (for complexes 1 and 3) and simultaneously considering the temperature dependent g factor (for complexes 2 and 4). Both the UV–Vis spectra and the magnetic properties of the solid solutions can be altered systematically by adjusting the Co(II)/Ni(II) ratio.
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