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Vogel, Sebastian; Bykov, Maxim; Bykova, Elena; Wendl, Sebastian; Kloss, Simon D.; Pakhomova, Anna; Chariton, Stella; Koemets, Egor; Dubrovinskaia, Natalia; Dubrovinsky, Leonid und Schnick, Wolfgang (2019): Boron Phosphorus Nitride at Extremes: PN6 Octahedra in the High-Pressure Polymorph beta-BP3N6. In: Angewandte Chemie-International Edition, Bd. 58, Nr. 27: S. 9060-9063

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Abstract

The high-pressure behavior of non-metal nitrides is of special interest for inorganic and theoretical chemistry as well as materials science, as these compounds feature intriguing elastic properties. The double nitride alpha-BP3N6 was investigated by in situ single-crystal X-ray diffraction (XRD) upon cold compression to a maximum pressure of about 42 GPa, and its isothermal bulk modulus at ambient conditions was determined to be 146(6) GPa. At maximum pressure the sample was laser-heated, which resulted in the formation of an unprecedented high-pressure polymorph, beta-BP3N6. Its structure was elucidated by single-crystal XRD, and can be described as a decoration of a distorted hexagonal close packing of N with B in tetrahedral and P in octahedral voids. Hence, beta-BP3N6 is the first nitride to contain PN6 octahedra, representing the much sought-after proof of principle for sixfold N-coordinated P that has been predicted for numerous high-pressure phases of nitrides.

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