Department of Chemistry and Key Laboratory of Advanced Energy Materials Chemistry, Nankai University, Tianjin 300071, People's Republic of China.
Dalton Trans. 2011 Apr 28;40(16):4155-61. doi: 10.1039/c0dt01746a. Epub 2011 Mar 8.
The structures and magnetic properties of four isomorphous nonanuclear heterometallic complexes [Na(2){Mn(3)(III)(μ(3)-O(2-))}(2)Ln(III)(hmmp)(6)(O(2)CPh)(4)(N(3))(2)]OH·0.5 CH(3)CN·1.5H(2)O are reported, where Ln(III) = Eu (1), Gd (2), Tb (3) and Dy (4), H(2)hmmp = 2-[(2-hydroxyethylimino)methyl]-6-methoxyphenol. Complexes 1-4 were prepared by the reactions of hmmpH(2) with a manganese salt and the respective lanthanide salt together with NaO(2)CPh and NaN(3). Single-crystal X-ray diffraction analyses reveal that the six Mn(III) and one Ln(III) metal topology in the aggregate can be described as a bitetrahedron. The two peripheral Mn(III)(3)(μ(3)-O(2-)) triangles are each bonded to a central Ln(III) ion with rare distorted octahedral geometry. The magnetic properties of all the complexes were investigated using variable temperature magnetic susceptibility and both antiferromagnetic and ferromagnetic interactions exist in the Mn(III)(3)(μ(3)-O(2-)) triangle. Weak ferromagnetic exchange between the Ln(III) and Mn(III) ions has been established for the corresponding Gd derivative. The Gd, Tb and Dy complexes show no evidence of slow relaxation behaviour above 2.0 K.
报道了四个同构的九核异金属配合物[Na(2){Mn(3)(III)(μ(3)-O(2-))}(2)Ln(III)(hmmp)(6)(O(2)CPh)(4)(N(3))(2)]OH·0.5 CH(3)CN·1.5H(2)O 的结构和磁性，其中 Ln(III) = Eu（1）、Gd（2）、Tb（3）和 Dy（4），H(2)hmmp = 2-[(2-羟乙基亚氨基)甲基]-6-甲氧基苯酚。配合物 1-4 是通过 hmmpH(2)与锰盐和相应的镧系元素盐与 NaO(2)CPh 和 NaN(3)一起反应制备的。单晶 X 射线衍射分析表明，聚合体中六个 Mn(III)和一个 Ln(III)金属拓扑结构可以描述为一个四面体。两个外围的Mn(III)(3)(μ(3)-O(2-))三角形各自与具有罕见的扭曲八面体几何形状的中心 Ln(III)离子键合。所有配合物的磁性均通过变温磁化率进行了研究，Mn(III)(3)(μ(3)-O(2-))三角形中存在反铁磁和铁磁相互作用。对于相应的 Gd 衍生物，已经建立了 Ln(III)和 Mn(III)离子之间的弱铁磁交换。Gd、Tb 和 Dy 配合物在 2.0 K 以上没有表现出缓慢弛豫行为的证据。
