Title
Semiclathrates of the GePTe system : synthesis and crystal structures Semiclathrates of the GePTe system : synthesis and crystal structures
Author
Faculty/Department
Faculty of Sciences. Physics
Publication type
article
Publication
Weinheim ,
Subject
Physics
Chemistry
Source (journal)
Chemistry: a European journal. - Weinheim
Volume/pages
17(2011) :20 , p. 5719-5726
ISSN
0947-6539
ISI
000290216000028
Carrier
E
Target language
English (eng)
Full text (Publishers DOI)
Affiliation
University of Antwerp
Abstract
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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