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首页> 外文期刊>Zeitschrift fur Anorganische und Allgemeine Chemie >Modular metal chalcogenide chemistry: Secondary building blocks as a basis of the silicate-type framework structure of CsLiU(PS _4) _2
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Modular metal chalcogenide chemistry: Secondary building blocks as a basis of the silicate-type framework structure of CsLiU(PS _4) _2

机译：模块化金属硫属化物化学：作为CsLiU（PS _4）_2的硅酸盐型骨架结构的基础的二级构件

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摘要

The novel uranium thiophosphate CsLiU(PS _4) _2 has been synthesized by reacting uranium metal, Cs _2S, Li _2S, S, and P _2S _5 at 700 °C in an evacuated silica tube. The crystal structure was determined by single-crystal X-ray diffraction techniques. CsLiU(PS _4) _2 crystallizes in the rhombohedral space group R$ar{3}$c (a = 15.2797(7) ?; c = 28.778(2) ?, V = 5818.7(5) ? ~3, Z = 18). The structure ofCsLiU(PS _4) _2 is a unique three-dimensional U(PS _4) _2 ~(2-) framework with large tunnels with an approximate diameter of 6.6 ? running parallel to the crystallographic c axis. The tunnels are filled with Cs ~+ cations. The smaller Li ~+ cations are located at tetrahedral sites at the periphery of the channels. In the structure of CsLiU(PS _4) _2 the uranium atoms are coordinated by thiophosphate groups in a pseudotetrahedral fashion, and the PS _4 groups act as linear connectors. Topologically, CsLiU(PS _4) _2 may be regarded a chalcogenide analogue of silicate frameworks, with the uranium atoms and PS _4 groups replacing silicon and oxygen atoms. Alternatively, CsLiU(PS _4) _2 may be viewed as a coordination polymer, which is formed in salt melts by the solid state equivalent of the "self-assembly" reactions in solution. Magnetic susceptibility measurements indicated Curie-Weiss-type behavior between 4 K and 300 K. The μ _(eff) of 2.83 μ _B at 300 K is in agreement with an f ~2 configuration of U ~(4+).
机译：新型硫代磷酸铀CsLiU（PS _4）_2是通过使铀金属，Cs _2S，Li _2S，S和P _2S _5在真空硅胶管中于700°C反应而合成的。通过单晶X射线衍射技术确定晶体结构。 CsLiU（PS _4）_2在菱形空间组R $ bar {3} $ c中结晶（a = 15.2797（7）？; c = 28.778（2）？，V = 5818.7（5）？〜3，Z = 18）。 CsLiU（PS _4）_2的结构是独特的三维U（PS _4）_2〜（2-）框架，具有大的隧道，直径约为6.6？。平行于晶体学c轴延伸。隧道中充满了Cs〜+阳离子。较小的Li +阳离子位于通道外围的四面体位置。在CsLiU（PS _4）_2的结构中，铀原子以拟四面体方式被硫代磷酸酯基团配位，而PS _4基团充当线性连接体。拓扑上，CsLiU（PS _4）_2可被视为硅酸盐骨架的硫族化物类似物，其中铀原子和PS _4基团取代了硅和氧原子。备选地，CsLiU（PS _4）_2可以看作是配位聚合物，它是通过与溶液中“自组装”反应的固态等同物在盐熔体中形成的。磁化率测量表明居里-魏斯型行为在4 K和300 K之间。在300 K时的2.83μ_B的μ_（eff）与U〜（4+）的f〜2构型一致。

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