Modular Metal Chalcogenide Chemistry: Secondary Building Blocks as a Basis of the Silicate-Type Framework Structure of CsLiU(PS4)2

作者：Neuhausen Christine; Rocker Frank; Tremel Wolfgang^*

来源：Zeitschrift fur Anorganische und Allgemeine Chemie, 2012, 638(2): 405-410.

DOI：10.1002/zaac.201100002

• Chalcogenides
• Uranium
• Thiophosphates
• Framework compounds
• Coordination polymers

The novel uranium thiophosphate CsLiU(PS4)2 has been synthesized by reacting uranium metal, Cs2S, Li2S, S, and P2S5 at 700 degrees C in an evacuated silica tube. The crystal structure was determined by single-crystal X-ray diffraction techniques. CsLiU(PS4)2 crystallizes in the rhombohedral space group R$\bar{3}$c (a = 15.2797(7) angstrom; c = 28.778(2) angstrom, V = 5818.7(5) angstrom 3, Z = 18). The structure ofCsLiU(PS4)2 is a unique three-dimensional U(PS4)22 framework with large tunnels with an approximate diameter of 6.6 angstrom 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(PS4)2 the uranium atoms are coordinated by thiophosphate groups in a pseudotetrahedral fashion, and the PS4 groups act as linear connectors. Topologically, CsLiU(PS4)2 may be regarded a chalcogenide analogue of silicate frameworks, with the uranium atoms and PS4 groups replacing silicon and oxygen atoms. Alternatively, CsLiU(PS4)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 CurieWeiss-type behavior between 4 K and 300 K. The mu eff of 2.83 mu B at 300 K is in agreement with an f2 configuration of U4+.

• 出版日期2012-2