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

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• 作者：Christopher Benndorf^a ; ^c ; Andrea Hohmann^b ; Peer Schmidt^b ; Hellmut Eckert^c ; ^d ; ^{eckerth@uni-muenster.de" class="auth_mail" title="E-mail the corresponding author} ; Dirk Johrendt^e ; Konrad Schä ; fer^a ; ^f ; Rainer Pö ; ttgen^a ; ^{pottgen@uni-muenster.de" class="auth_mail" title="E-mail the corresponding author}
• 关键词：Polyphosphide ; Solid state NMR spectroscopy ; Thermochemistry
• 刊名：Journal of Solid State Chemistry
• 出版年：2016
• 出版时间：March 2016
• 年：2016
• 卷：235
• 期：Complete
• 页码：139-144
• 全文大小：1677 K

文摘

Phase pure polycrystalline PbP₇ 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 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>550 K 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.