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Bertschler, Eva-Maria; Niklaus, Robin; Schnick, Wolfgang ORCID: 0000-0003-4571-8035 (2018): Reversible Polymerization of Adamantane-type [P4N10](10-) Anions to Honeycomb-type [P2N5](5-) Layers under High-Pressure. In: Chemistry - A European Journal, Vol. 24, No. 3: pp. 736-742
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The high-pressure polymorph Li5P2N5 of Li10P4N10 (='' 2 Li5P2N5 '') was synthesized by high-pressure/high-temperature reaction of LiPN2 and Li7PN4 or beta-Li10P4N10 at 9 GPa, using the Li3N self-flux method in a Walker-type multianvil assembly. Li5P2N5 is the first lithium nitridophosphate with a layered structure and is made up of corner sharing PN4 tetrahedra forming a corrugated honeycomb-type layer of linked sechser-rings in chair conformation. The arrangement of the P atoms is analogous to that of black phosphorus. The structure was elucidated from single-crystal X-ray data. To confirm the structure Rietveld refinement, Li-6, Li-7 and P-31 solid-state NMR spectroscopy were conducted. To corroborate Li5P2N5 as the corresponding high-pressure polymorph of beta-Li10P4N10 DFT calculations and temperature dependent X-ray powder diffraction were carried out. DFT calculations estimated the transition pressure to 6.5 GPa (without accounting for temperature), which is in line with the synthesis pressure.