Abstract
Pure, stoichiometric, hydrogen-free, and crystalline phosphorus nitride P3N5 has been obtained for the first time by reaction of (PNCl2)3 and NH4Cl between 770 and 1050 K. The compound has been characterized by elemental analyses, 31P and 15N MAS NMR, EXAFS, IR spectroscopy, X-ray powder diffraction, and electron microscopy. In the solid a three-dimensional cross-linked network structure of corner sharing PN4 tetrahedra has been identified with 2/5 of the nitrogen atoms bonded to three P atoms and 3/5 of the nitrogen atoms bonded to two P atoms. By electron diffraction (ED) and high-resolution transmission electron microscopy (HRTEM) two distinguishable modifications α-P3N5 and β-P3N5 have been identified which differentiate only by the stacking order of identical sheets similar to the polytypes of SiC.
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