State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, The Chinese Academy of Sciences, Fuzhou, Fujian 350002, China.
Dalton Trans. 2013 Apr 14;42(14):4908-14. doi: 10.1039/c2dt32739b.
Reactions of [Mn6O2(piv)10(py)2.5(piv)1.5], Ln(NO3)3·6H2O and N-mdeaH2 in MeCN in the presence of Me3SiCl generated a family of octanuclear Mn/Ln complexes [Mn6(III)Mn(II)Ln(N-mdea)3(N-mdeaH)(piv)8O2(OH)3(NO3)(H2O)]·xCH3CN·xH2O [Ln = Gd (1), Dy (2), Er (3), pivH = pivalic acid, N-mdeaH2 = N-methyl diethanolamine]. Each complex possesses a Mn6(III)Mn(II)Ln(μ3-O)2(μ3-OH)3 core containing two butterfly-like subunits of [Mn3Ln(μ3-OH)2] and [Mn4(μ3-O)2] sharing a common vertex, and an outer Mn atom ligated to one of the subunits through a μ3-OH(-) ligand. The core topology represents a new Mn/Ln core type. The magnetic susceptibility study of 1-3 indicates the presence of dominant antiferromagnetic interactions within the complexes. For complex 1, which contains an isotropic Gd(III) atom, fitting of the obtained M/(NμB) vs. H/T data gave S = 4, g = 1.90, and D = -0.31 cm(-1). The results were further supported by ac data. Complex exhibits out-of-phase ac susceptibility signals, indicating it may be a SMM.
在 MeCN 中，[Mn6O2(piv)10(py)2.5(piv)1.5]、Ln(NO3)3·6H2O 和 N-mdeaH2 与 Me3SiCl 的反应生成了一系列八核 Mn/Ln 配合物 [Mn6(III)Mn(II)Ln(N-mdea)3(N-mdeaH)(piv)8O2(OH)3(NO3)(H2O)]·xCH3CN·xH2O [Ln = Gd (1)、Dy (2)、Er (3)、pivH = 丙酮酸、N-mdeaH2 = N-甲基二乙醇胺]。每个配合物都具有一个 Mn6(III)Mn(II)Ln(μ3-O)2(μ3-OH)3 核，其中包含两个蝶形亚基 [Mn3Ln(μ3-OH)2] 和 [Mn4(μ3-O)2]，它们共享一个公共顶点，一个外部 Mn 原子通过一个 μ3-OH(-) 配体与其中一个亚基配位。核拓扑结构代表了一种新的 Mn/Ln 核类型。1-3 的磁化率研究表明，配合物内部存在主导的反铁磁相互作用。对于含有各向同性 Gd(III)原子的 1 号配合物，对获得的 M/(NμB)与 H/T 数据的拟合给出了 S = 4、g = 1.90 和 D = -0.31 cm(-1)。交流数据进一步支持了这些结果。配合物表现出出相交流磁化率信号，表明它可能是一个 SMM。
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