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Title
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Semiclathrates of the GePTe system : synthesis and crystal structures
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Author
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Abstract
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| Novel compounds [Ge46−xPx]Tey (13.9≤x≤15.6, 5.92≤y≤7.75) with clathrate-like structures have been prepared and structurally characterized. They crystallize in the space group Fmequation image with the unit cell parameter changing from 20.544(2) to 20.698(2) Å (Z=8) on going from x=13.9 to x=15.6. Their crystal structure is composed of a covalently bonded Ge[BOND]P framework that hosts tellurium atoms in the guest positions and can be viewed as a peculiar variant of the type I clathrate superstructure. In contrast to the conventional type I clathrates, [Ge46−xPx]Tey contain tricoordinated (3b) atoms and no vacancies in the framework positions. As a consequence of the transformation of the framework, the majority of the guest tellurium atoms form a single covalent bond with the host framework and thus the title compounds are the first representative of semiclathrates with covalent bonding. A comparison is made with silicon clathrates and the evolution of the crystal structure upon changing the tellurium content is discussed. |
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Language
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English
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Source (journal)
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Chemistry: a European journal. - Weinheim
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Publication
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Weinheim
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2011
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ISSN
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0947-6539
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DOI
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10.1002/CHEM.201003553
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Volume/pages
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17
:20
(2011)
, p. 5719-5726
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ISI
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000290216000028
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Full text (Publisher's DOI)
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