Dominik Baumann

Pentacoordinate phosphorus in a high-pressure polymorph of phosphorus nitride imide P4N6(NH).

Coordination numbers higher than usual are often associated with superior mechanical properties. In this contribution we report on the synthesis of the high-pressure polymorph of highly condensed phosphorus nitride imide P4 N6 (NH) representing a new framework topology. This is the first example of phosphorus in trigonal-bipyramidal coordination being observed in an inorganic network structure. We were able to obtain single crystals and bulk samples of the compound employing the multi-anvil technique. γ-P4 N6 (NH) has been thoroughly characterized using X-ray diffraction, solid-state NMR and FTIR spectroscopy. The synthesis of γ-P4 N6 (NH) gives new insights into the coordination chemistry of phosphorus at high pressures. The synthesis of further high-pressure phases with higher coordination numbers exhibiting intriguing physical properties seems within reach.

High-Pressure Polymorph of Phosphorus Nitride Imide HP4N7 Representing a New Framework Topology

A new polymorph of phosphorus nitride imide HP4N7 has been synthesized under high-pressure/high-temperature conditions from P3N5 and NH4Cl at 6 GPa and temperatures between 800 and 1300 °C. Its crystal structure was elucidated using single-crystal X-ray diffraction data. β-HP4N7 (space group C2/c, no. 15, Z = 4, a = 12.873(2) Å, b = 4.6587(4) Å, c = 8.3222(8) Å, β = 102.351(3)°, R1 = 0.0485, wR2 = 0.1083) crystallizes in a new framework structure type that is made up of all-side vertex-sharing PN4 tetrahedra. The topology of the network is represented by the point symbol (3(2).4(2).5(2).6(3).7)(3(4).4(4).5(4).6(3)), and it has not been identified in other compounds so far. Structural differences between the two polymorphs of HP4N7 as well as the topological relationship to the recently discovered high-pressure polymorph β-HPN2 are discussed. Additionally, FTIR and solid-state NMR spectroscopy are used to corroborate the results of the structure determination.

Reversible high-pressure phase transition in LaN

In situ high-pressure X-ray powder diffraction experiments on LaN up to 60.1 GPa at ambient temperature in a diamond-anvil cell revealed a reversible, first-order structural phase transition starting at ∼22.8 GPa and completed at ∼26.5 GPa from the ambient cubic phase (Fm3¯m, no. 225) to a tetragonal high-pressure phase (P4/nmm, no. 19, a = 4.1060(6), c = 3.0446(6) A, Z = 2, wRp = 0.011), which has not been claimed in theoretical predictions. HP-LaN is isotypic with a high-pressure polymorph of BaO, which crystallizes in a tetragonally distorted CsCl-type structure. The phase transition is accompanied by a volume collapse of about 11% which corresponds well with the reported data on HP-BaO. A linear extrapolation of the c/a ratio of the tetragonally distorted CsCl-type sub-cell reaches a value c/a = 1 of cubic CsCl-type HP-LaN at 91(12) GPa. In addition, the compressibility of LaN was investigated and resulted in a bulk modulus for the ambient pressure phase of B0 = 135(3) GPa and B′ = 5.0(5) after fittin...

A High‐Pressure Polymorph of Phosphorus Oxonitride with the Coesite Structure

The chemical and physical properties of phosphorus oxonitride (PON) closely resemble those of silica, to which it is isosteric. A new high-pressure phase of PON is reported herein. This polymorph, synthesized by using the multianvil technique, crystallizes in the coesite structure. This represents the first occurrence of this very dense network structure outside of SiO2 . Phase-pure coesite PON (coe-PON) can be synthesized in bulk at pressures above 15 GPa. This compound was thoroughly characterized by means of powder X-ray diffraction, DFT calculations, and FTIR and MAS NMR spectroscopy, as well as temperature-dependent diffraction. These results represent a major step towards the exploration of the phase diagram of PON at very high pressures and the possibly synthesis of a stishovite-type PON containing hexacoordinate phosphorus.

Crystal structures of cristobalite-type and coesite-type PON redetermined on the basis of single-crystal X-ray diffraction data

The crystal structures of two phosphorus oxonitride polymorphs (cristobalite- and coesite-type) were redetermined by means of single-crystal X-ray diffraction data.

Stishovite's Relative: A Post-Coesite Form of Phosphorus Oxonitride

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 K0 =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.