High-Pressure Synthesis of the β-Zn₃N₂ Nitride and the α-ZnN₄ and β-ZnN₄ Polynitrogen Compounds

High-pressure nitrogen chemistry has expanded at a formidable rate over the past decade, unveiling the chemical richness of nitrogen. Here, the Zn-N system is investigated in laser-heated diamond anvil cells by synchrotron powder and single-crystal X-ray diffraction, revealing three hitherto unobserved nitrogen compounds: β-Zn₃N₂, α-ZnN₄, and β-ZnN₄, formed at 35.0, 63.5, and 81.7 GPa, respectively. Whereas β-Zn₃N₂ contains the N^3- nitride, both ZnN₄ solids are found to be composed of polyacetylene-like [N₄]_∞^2- chains. Upon the decompression of β-ZnN₄ below 72.7 GPa, a first-order displacive phase transition is observed from β-ZnN₄ to α-ZnN₄. The α-ZnN₄ phase is detected down to 11.0 GPa, at lower pressures decomposing into the known α-Zn₃N₂ (space group Ia3̅) and N₂. The equations of states of β-ZnN₄ and α-ZnN₄ are also determined, and their bulk moduli are found to be K₀ = 126(9) GPa and K₀ = 76(12) GPa, respectively. Density functional theory calculations were also performed and provide further insight into the Zn-N system. Moreover, comparing the Mg-N and Zn-N systems underlines the importance of minute chemical differences between metal cations in the resulting synthesized phases.