Three-Dimensional 3d−4f Polymers Containing Heterometallic Rings: Syntheses, Structures, and Magnetic Properties

Two novel three-dimensional (3D) 3d−4f mixed complexes [Ln(H2O)4][Ni2TTHA(SCN)2]·H3O+ [Ln = Pr (1), Ce (2); H6TTHA =
triethylenetetraaminehexaacetic acid], based on the building
blocks of [Ni2TTHA(SCN)2]4-, were synthesized and characterized
by X-ray crystal diffraction and magnetic properties. The single-crystal structures show that these complexes form a 3D framework,
comprised of an unusual infinite one-dimensional chain based on
heterometallic Ln2Ni2 rings. The temperature-dependent magnetic
susceptibilities were analyzed by an approximate model, leading
to g = 2.06. Δ = 2.83, zJ‘ = −0.6 cm-1 for complex 1 and g =
2.07, Δ = 1.00, zJ‘ = −0.5 cm-1 for complex 2.

两种新型三维（3D）3d-4f杂金属配合物[Ln(H₂O)₄][Ni₂TTHA(SCN)₂]·H₃O⁺[Ln=Pr(1)、Ce(2)；H₆TTHA=三亚乙基四胺六乙酸]，以[Ni₂TTHA(SCN)₂]⁴⁻为构筑单元完成合成，并通过X射线单晶衍射与磁学性质表征。单晶结构解析结果表明，该类配合物构筑得到三维骨架，其结构由基于异金属Ln₂Ni₂环的非常规无限一维链构成。采用近似模型对变温磁化率数据进行拟合分析，得到配合物1的拟合参数为g=2.06、Δ=2.83、zJ’=-0.6 cm⁻¹，配合物2的拟合参数为g=2.07、Δ=1.00、zJ’=-0.5 cm⁻¹。