Breaking the Tetra-Coordinated Framework Rule: New Clathrate Ba8M24P28+δ ( M =Cu/Zn)
- Department of Chemistry, The University of California, Davis, One Shields Avenue Davis CA 95616 USA
- Department of Materials Science and Engineering, The University of California, Davis, One Shields Avenue Davis CA 95616 USA
A new clathrate type has been discovered in the Ba/Cu/Zn/P system. The crystal structure of the Ba8M24P28+δ (M=Cu/Zn) clathrate is composed of the pentagonal dodecahedra common to clathrates along with a unique 22-vertex polyhedron with two hexagonal faces capped by additional partially occupied phosphorus sites. This is the first example of a clathrate compound where the framework atoms are not in tetrahedral or trigonal-pyramidal coordination. In Ba8M24P28+δ a majority of the framework atoms are five- and six-coordinated, a feature more common to electron-rich intermetallics. The crystal structure of this new clathrate was determined by a combination of X-ray and neutron diffraction and was confirmed with solid-state 31P NMR spectroscopy. Based on chemical bonding analysis, the driving force for the formation of this new clathrate is the excess of electrons generated by a high concentration of Zn atoms in the framework. The rattling of guest atoms in the large cages results in a very low thermal conductivity, a unique feature of the clathrate family of compounds.
- Research Organization:
- Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
- Sponsoring Organization:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI ID:
- 1345411
- Journal Information:
- Angewandte Chemie (International Edition), Vol. 56, Issue 9; ISSN 1433-7851
- Publisher:
- Wiley
- Country of Publication:
- United States
- Language:
- ENGLISH
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