Li12P3N9 with Non-Condensed [P3N9](12-)-Rings and its High-Pressure Polymorph Li4PN3 with Infinite Chains of PN4-Tetrahedra

Bertschler, Eva-Maria; Niklaus, Robin und Schnick, Wolfgang (2017): Li12P3N9 with Non-Condensed [P3N9](12-)-Rings and its High-Pressure Polymorph Li4PN3 with Infinite Chains of PN4-Tetrahedra. In: Chemistry-A European Journal, Bd. 23, Nr. 40: S. 9592-9599

Abstract

Li12P3N9 was synthesized by solid-state reaction of Li3N and P3N5 at 790 degrees C. It is made up of non-condensed [P3N9](12-) dreier-rings of PN4-tetrahedra. The corresponding high-pressure polymorph, Li4PN3, was synthesized under high-pressure/high-temperature conditions from Li12P3N9 or LiPN2 and Li7PN4 at 6 or 7 GPa, respectively, using the multi-anvil technique. Li4PN3 is the first lithium catena-nitridophosphate and contains PN3 zweier-chains of corner sharing PN4-tetrahedra. To confirm the structure elucidated from single-crystal X-ray data, Rietveld refinement, Li-6, Li-7, and P-31 solid-state NMR spectroscopy, FTIR spectroscopy and EDX measurements were carried out. To examine the phase transition of Li12P3N9 to Li4PN3 at 6 GPa and to corroborate the latter as the corresponding high-pressure polymorph, DFT calculations were conducted. Electronic band gap and electron localization function (ELF) calculations were carried out to elucidate the electronic properties and bonding behavior of both polymorphs.

• Dokumententyp: Zeitschriftenartikel
• Fakultät: Chemie und Pharmazie > Department Chemie
• Themengebiete: 500 Naturwissenschaften und Mathematik > 540 Chemie
• ISSN: 0947-6539
• Sprache: Englisch