The Synthesis, Crystal Structure, and Magnetic Properties of Mono-Scorpionate Eu(III) Complexes

Kira E. Vostrikova, Taisiya S. Sukhikh, Alexander N. Lavrov
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Abstract

Three Eu3+ complexes containing a neutral tripodal ligand possessing a predictable coordination mode have been obtained and studied. The trispyrazolylmethane complexes have an aqua ligand in the coordination sphere, forming both the mononuclear species [Eu(HCPz3)H2O(NO3)3] and the dimer [Eu(HCPz3)H2O(CF3SO3)3]2, having a Chinese lantern structure, whereas the use of the methylated tripod leads to the water-free complex, [Eu(HC(PzMe2)3)(NO3)3]. A qualitative analysis of the magnetic susceptibility of polycrystalline samples demonstrated that the magnetic properties can be described using a simple Van Vleck formula with spin–orbit coupling parameter (λ = 383 ÷ 406 cm−1) close to the values for free Eu3+ ions. The stereochemical analysis of the coordination environment of [Ln(HC(PzMe2)3)(NO3)3] has shown that these complexes can be used as diamagnetic model systems to obtain information on the crystal field effects in the paramagnetic monoradical complexes, [LnRad(NO3)3], since both types of compounds have the same type of coordination polyhedron (symmetry point group D3h) and very close Ln–donor atom distances.
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单蝎酸Eu(III)配合物的合成、晶体结构和磁性能
获得并研究了三种含中性三足配体的Eu3+配合物,它们具有可预测的配位模式。三吡唑基甲烷配合物在配位球中有一个水配体,形成单核物质[Eu(HCPz3)H2O(NO3)3]和二聚体[Eu(HCPz3)H2O(CF3SO3)3]2,具有中国灯结构,而使用甲基化的三脚架导致无水配合物[Eu(HC(PzMe2)3)(NO3)3]。对多晶样品磁化率的定性分析表明,其磁性能可以用一个简单的Van Vleck公式来描述,其自旋-轨道耦合参数(λ = 383 ÷ 406 cm−1)接近自由Eu3+离子的值。对[Ln(HC(PzMe2)3)(NO3)3]配位环境的立体化学分析表明,由于两类化合物具有相同类型的配位多面体(对称点群D3h)和非常接近的给体原子距离,这些配合物可以作为反磁模型体系来获得顺磁单自由基配合物[LnRad(NO3)3]中的晶体场效应信息。
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