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Title: Breaking the Tetra-Coordinated Framework Rule: New Clathrate Ba 8 M 24P 28+δ ( M =Cu/Zn)

Abstract

A new clathrate type has been discovered in the Ba/Cu/Zn/P system. The crystal structure of the Ba 8M 24P 28+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 Ba 8M 24P 28+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.

Authors:
 [1];  [1];  [2];  [2]; ORCiD logo [1]
  1. Department of Chemistry, The University of California, Davis, One Shields Avenue Davis CA 95616 USA
  2. Department of Materials Science and Engineering, The University of California, Davis, One Shields Avenue Davis CA 95616 USA
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1345411
Resource Type:
Journal Article
Resource Relation:
Journal Name: Angewandte Chemie (International Edition); Journal Volume: 56; Journal Issue: 9
Country of Publication:
United States
Language:
ENGLISH
Subject:
36 MATERIALS SCIENCE

Citation Formats

Dolyniuk, Juli-Anna, Zaikina, Julia V., Kaseman, Derrick C., Sen, Sabyasachi, and Kovnir, Kirill. Breaking the Tetra-Coordinated Framework Rule: New Clathrate Ba8M24P28+δ ( M =Cu/Zn). United States: N. p., 2017. Web. doi:10.1002/anie.201611510.
Dolyniuk, Juli-Anna, Zaikina, Julia V., Kaseman, Derrick C., Sen, Sabyasachi, & Kovnir, Kirill. Breaking the Tetra-Coordinated Framework Rule: New Clathrate Ba8M24P28+δ ( M =Cu/Zn). United States. doi:10.1002/anie.201611510.
Dolyniuk, Juli-Anna, Zaikina, Julia V., Kaseman, Derrick C., Sen, Sabyasachi, and Kovnir, Kirill. Wed . "Breaking the Tetra-Coordinated Framework Rule: New Clathrate Ba8M24P28+δ ( M =Cu/Zn)". United States. doi:10.1002/anie.201611510.
@article{osti_1345411,
title = {Breaking the Tetra-Coordinated Framework Rule: New Clathrate Ba8M24P28+δ ( M =Cu/Zn)},
author = {Dolyniuk, Juli-Anna and Zaikina, Julia V. and Kaseman, Derrick C. and Sen, Sabyasachi and Kovnir, Kirill},
abstractNote = {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.},
doi = {10.1002/anie.201611510},
journal = {Angewandte Chemie (International Edition)},
number = 9,
volume = 56,
place = {United States},
year = {Wed Jan 18 00:00:00 EST 2017},
month = {Wed Jan 18 00:00:00 EST 2017}
}