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![The Synthesis of [Sn10SiSiMe334]2- Using a Metastable SnI Halide Solution Synthesized via a Co-condensation Technique](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F54498.jpg&w=3840&q=50)
The Synthesis of [Sn10SiSiMe334]2- Using a Metastable SnI Halide Solution Synthesized via a Co-condensation Technique
Published on: November 28, 2016
[Tl7]7- Clusters in Mixed Alkali Metal Thallides Cs7.29K5.71Tl13 and Cs3.45K3.55Tl7
Vanessa F Schwinghammer1, Stefanie Gärtner1,2
1Institute of Inorganic Chemistry, University of Regensburg, Universitätsstraße 31, 93053 Regensburg, Germany.
Abstract:
Investigations in the ternary system Cs-K-Tl resulted in the unexpected formation of new ternary thallides Cs7.29K5.71Tl13 and Cs3.45K3.55Tl7. Single crystal X-ray structure analyses of both compounds reveal the presence of isolated Tl cluster units. Cs7.29K5.71Tl13 crystallizes in the monoclinic space group C2/c (a = 30.7792(9) Å, b = 11.000(2) Å, c = 14.0291(4) Å, β = 112.676(4)°, Z = 4) and contains [Tl6]6- and [Tl7]7- clusters as thallium subunits. Cs3.45K3.55Tl7 crystallizes in the tetragonal space group I41/a (a = 13.6177(2) Å, c = 25.5573(8) Å, Z = 8) and contains [Tl7]7- clusters exclusively. The formation of Cs7.29K5.71Tl13 is obtained after slow cooling in addition to that of Cs3.45K3.55Tl7 and can be suppressed by quenching the stoichiometric mixture. First dissolution experiments in liquid ammonia suggest thallium and amide as final oxidation products. Full relativistic band structure calculations of Cs4K3Tl7 and Cs8K5Tl13 showed a (pseudo) band gap around EF for both compounds.
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