2D {sup 31}P solid state NMR spectroscopy, electronic structure and thermochemistry of PbP{sub 7}
- Institut für Anorganische und Analytische Chemie, Universität Münster, Corrensstraße 30, 48149 Münster (Germany)
- Brandenburgische Technische Universität Cottbus-Senftenberg, Fakultät für Naturwissenschaften, Postfach 101548, 01958 Senftenberg (Germany)
- Institut für Physikalische Chemie, Universität Münster, Corrensstraße 30, 48149 Münster (Germany)
- Department Chemie, Ludwig-Maximilians-Universität München, Butenandtstraße 5-13, D-81377 München (Germany)
Phase pure polycrystalline PbP{sub 7} was prepared from the elements via a lead flux. Crystalline pieces with edge-lengths up to 1 mm were obtained. The assignment of the previously published {sup 31}P 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 {sup 31}P chemical shift and structural parameters. PbP{sub 7} decomposes incongruently under release of phosphorus forming liquid lead as remainder. The thermal decomposition starts at T>550 K with a vapor pressure almost similar to that of red phosphorus. Electronic structure calculations reveal PbP{sub 7} as a semiconductor according to the Zintl description and clearly shows the stereo-active Pb-6s{sup 2} lone pairs in the electron localization function ELF. - Graphical abstract: Coordination of the lead atoms in PbP{sub 7}.
- OSTI ID:
- 22577795
- Journal Information:
- Journal of Solid State Chemistry, Vol. 235; Other Information: Copyright (c) 2015 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Country of input: International Atomic Energy Agency (IAEA); ISSN 0022-4596
- Country of Publication:
- United States
- Language:
- English
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