The average and local structure of the oxides Ba2SiO4, BaAl2O4, SrAl2O4, and Y2SiO5 are examined to evaluate crystal rigidity in light of recent studies suggesting that highly connected and rigid structures yield the best phosphor hosts. Simultaneous momentum-space refinements of synchrotron X-ray and neutron scattering yield accurate average crystal structures, with reliable atomic displacement parameters. The Debye temperature ΘD, which has proven to be a useful proxy for structural rigidity, is extracted from the experimental atomic displacement parameters and compared with predictions from density functional theory calculations and experimental low-temperature heat capacity measurements. The role of static disorder on the measured displacement parameters, and the resulting Debye temperatures, are also analyzed using pair distribution function of total neutron scattering, as refined over varying distance ranges of the pair distribution function. The interplay between optimal bonding in the structure, structural rigidity, and correlated motion in these structures is examined, and the different contributions are delineated.

Nitridophosphates and phosphorus nitrides are thoroughly investigated classes of nitrides. During thirty years of research, the methods for their synthesis evolved from the condensation of molecular precursors at moderate temperatures and ambient pressures to state‐of‐the‐art high‐pressure and high‐temperature processes. Landmark breakthroughs made in recent years led to a comprehension‐based proficiency in nitridophosphate synthesis that is illustrated by the large compositional and structural diversity of the nitridophosphates known today. Herein, we review the advances made in synthesis with regard to the prevalent problem of nitride synthesis: the susceptibility of nitride ions to oxidation.

Developing a synthetic method to target an broad spectrum of unknown phases can lead to fascinating discoveries. The preparation of the first rare-earth-metal nitridophosphate LiNdP4 N8 is reported. High-pressure solid-state metathesis between LiPN2 and NdF3 was employed to yield a highly crystalline product. The in situ formed LiF is believed to act both as the thermodynamic driving force and as a flux to aiding single-crystal formation in dimensions suitable for crystal structure analysis. Magnetic properties stemming from Nd(3+) ions were measured by SQUID magnetometry. LiNdP4 N8 serves as a model system for the exploration of rare-earth-metal nitridophosphates that may even be expanded to transition metals. High-pressure metathesis enables the systematic study of these uncharted regions of nitride-based materials with unprecedented properties.

High-pressure metathesis was proposed to be a gateway to the elusive class of rare-earth nitridophosphates. With this method the first ternary compounds of this class with sum formula RE2P3N7 were prepared, a melilite-type with RE = Pr, Nd, Sm, Eu, Ho, Yb (Ho2P3N7: P4̅21m, a = 7.3589(2), c = 4.9986(2) Å, Z = 2) and a Ba2Cu[Si2O7] structure type with RE = La, Ce, Pr (Pr2P3N7: monoclinic, C2/c, a = 7.8006(3), b = 10.2221(3), c = 7.7798(3) Å, β = 111.299(1)°, Z = 4). The phase relation between the two structure types was prior unknown and is here evidenced by experimental data as well as density functional theory calculations performed for the Pr2P3N7 compounds. Adequate classification of both structures types with regard to Liebau nomenclature, vertex symbol, and point symbol is made. Additionally, the tiling patterns of the monolayered structures are deducted. We demonstrate that high-pressure metathesis offers a systematic access to rare-earth nitridophosphates with an atomic ratio of P/N between 1/2 and 1/4.