CaLi2PN3 - A Quaternary Chain-Type Nitridophosphate by Medium-Pressure Synthesis.

Abstract

Nitridophosphates are in the focus of current research interest due to their structural versatility and properties, such as ion conductivity, ultra-incompressibility and luminescent properties when doped with suitable activator ions. Multinary representatives often require thorough investigation due to the competition with the thermodynamically more stable binary and ternary compounds. Another point of concern is the synthetic control of structural details, which is usually limited by conventional bottom-up syntheses. In this study, we report on the synthesis and characterization of the quaternary nitridophosphate CaLi2PN3. Various synthesis protocols were used for the preparation of CaLi2PN3, including the novel nitridophosphate double salt approach. The crystal structure was solved and refined from single-crystal X-ray diffraction data and confirmed by Rietveld refinement, solid-state NMR spectroscopy, EDX measurements and low-cost crystallographic calculations. The experimental results were corroborated by DFT calculations, which revealed the electronic band structure. Formation energy calculations allowed conclusions to be drawn about the stability in comparison to the initial ternary nitridophosphates. The synthesis of CaLi2PN3 exemplifies the enormous potential of medium-pressure syntheses in the field of nitridophosphate research. Furthermore, the presented new synthesis route allows a certain degree of structural control, which is a promising addition to previous synthesis strategies in nitridophosphate chemistry.