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.

中文翻译：

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CaLi2PN3 – 中压合成的季链型亚氮磷酸盐


亚硝基磷酸盐由于其结构的多功能性和特性而成为当前研究兴趣的焦点，例如掺杂合适的活化剂离子时的离子电导率、超不可压缩性和发光特性。由于与热力学上更稳定的二元和三元化合物的竞争，多元代表通常需要进行彻底的研究。另一个值得关注的问题是结构细节的合成控制，这通常受到传统的自下而上合成的限制。在这项研究中，我们报道了季氮磷酸盐 CaLi2PN3 的合成和表征。 CaLi2PN3 的制备采用了多种合成方案，包括新型亚氮磷酸盐复盐方法。根据单晶 X 射线衍射数据解析和精炼晶体结构，并通过 Rietveld 精修、固态 NMR 光谱、EDX 测量和低成本晶体学计算确认。 DFT计算证实了实验结果，揭示了电子能带结构。形成能计算可以得出与初始三元硝基磷酸盐相比的稳定性的结论。 CaLi2PN3 的合成体现了中压合成在亚氮磷酸盐研究领域的巨大潜力。此外，所提出的新合成路线允许一定程度的结构控制，这对于亚氮磷酸盐化学中先前的合成策略来说是一个有希望的补充。