2D 31P solid state NMR spectroscopy, electronic structure and thermochemistry of PbP7

Phase pure polycrystalline PbP7 was prepared from the elements via a lead flux. Crystalline pieces with edge-lengths up to 1mm were obtained. The assignment of the previously published 31P solid state NMR spectrum to the seven distinct crystallographic sites was accomplished by radio-frequency drive...

Full description

Saved in:
Bibliographic Details
Published in:Journal of solid state chemistry 2016-03, Vol.235, p.139-144
Main Authors: Benndorf, Christopher, Hohmann, Andrea, Schmidt, Peer, Eckert, Hellmut, Johrendt, Dirk, Schäfer, Konrad, Pöttgen, Rainer
Format: Article
Language:English
Subjects:
Polyphosphide
Solid state NMR spectroscopy
Thermochemistry
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:Phase pure polycrystalline PbP7 was prepared from the elements via a lead flux. Crystalline pieces with edge-lengths up to 1mm were obtained. The assignment of the previously published 31P solid state NMR spectrum to the seven distinct crystallographic sites was accomplished by radio-frequency driven dipolar recoupling (RFDR) experiments. As commonly found in other solid polyphosphides there is no obvious correlation between the 31P chemical shift and structural parameters. PbP7 decomposes incongruently under release of phosphorus forming liquid lead as remainder. The thermal decomposition starts at T>550K with a vapor pressure almost similar to that of red phosphorus. Electronic structure calculations reveal PbP7 as a semiconductor according to the Zintl description and clearly shows the stereo-active Pb-6s2 lone pairs in the electron localization function ELF. Coordination of the lead atoms in PbP7. [Display omitted]
ISSN:0022-4596
1095-726X
DOI:10.1016/j.jssc.2015.12.028