Journal
JOURNAL OF ORGANOMETALLIC CHEMISTRY
Volume 611, Issue 1-2, Pages 543-546Publisher
ELSEVIER SCIENCE SA
DOI: 10.1016/S0022-328X(00)00404-6
Keywords
silicon clathrate; high-pressure synthesis; barium; Si-sp(3) network
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A new silicon clathrate Ba24Si100 was prepared from a stoichiometric mixture of 12 BaSi2 and 76 Si in a molar ratio using a high pressure of 1.5 GPa at 800 degrees C. The X-ray Rietveld analysis revealed that Ba24Si25, was isotypic with K8Sn25, consisting of Ba containing dodecahedral silicon cages, Ba@Si-20, which are linked by sharing the pentagonal faces. A chiral zeolite-like network was formed; the rest of Ba atoms occupied the resulting interstices of Si-20 open-cages and Si-8 pseudo-cubic spaces. The synthesis using a pressure higher than 3 GPa at 800 degrees C gave a mixture of the type I silicon clathrate Ba8Si46 and Si. It should be noted that the germanium analog Ba24Ge100 was prepared by a. simple are-melting under Ar atmosphere, while the silicon analog required a moderately high pressure for the preparation. Ba24Si100 showed a metallic conductivity (C) 2000 Elsevier Science S.A. All rights reserved.
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