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Vogel, Sebastian; Baumann, Dominik; Niklaus, Robin; Bykova, Elena; Bykov, Maxim; Dubrovinskaia, Natalia; Dubrovinsky, Leonid; Schnick, Wolfgang (2018): Stishovite's Relative: A Post-Coesite Form of Phosphorus Oxonitride. In: Angewandte Chemie - International Edition, Vol. 57, No. 22: pp. 6691-6695
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Abstract

Phosphorus oxonitride (PON) is isoelectronic with SiO2 and may exhibit a similar broad spectrum of intriguing properties as silica. However, PON has only been sparsely investigated under high-pressure conditions and there has been no evidence on a PON polymorph with a coordination number of P greater than 4. Herein, we report a post-coesite (pc) PON polymorph exhibiting a stishovite-related structure with P in a (5+1) coordination. The pc-PON was synthesized using the multianvil technique and characterized by powder X-ray diffraction, solid-state NMR spectroscopy, TEM measurements and in situ synchrotron X-ray diffraction in diamond anvil cells. The structure model was verified by single-crystal X-ray diffraction at 1.8 GPa and the isothermal bulk modulus of pc-PON was determined to K-0=163(2) GPa. Moreover, an orthorhombic PON polymorph (o-PON) was observed under high-pressure conditions and corroborated as the stable modification at pressures above 17 GPa by DFT calculations.