High‐Pressure Synthesis of Metal–Inorganic Frameworks Hf₄N₂₀⋅N₂, WN₈⋅N₂, and Os₅N₂₈⋅3 N₂ with Polymeric Nitrogen Linkers

Abstract

Polynitrides are intrinsically thermodynamically unstable at ambient conditions and require peculiar synthetic approaches. Now, a one-step synthesis of metal-inorganic frameworks Hf₄ N₂₀ ⋅N₂ , WN₈ ⋅N₂ , and Os₅ N₂₈ ⋅3 N₂ via direct reactions between elements in a diamond anvil cell at pressures exceeding 100 GPa is reported. The porous frameworks (Hf₄ N₂₀ , WN₈ , and Os₅ N₂₈ ) are built from transition-metal atoms linked either by polymeric polydiazenediyl (polyacetylene-like) nitrogen chains or through dinitrogen units. Triply bound dinitrogen molecules occupy channels of these frameworks. Owing to conjugated polydiazenediyl chains, these compounds exhibit metallic properties. The high-pressure reaction between Hf and N₂ also leads to a non-centrosymmetric polynitride Hf₂ N₁₁ that features double-helix catena-poly[tetraz-1-ene-1,4-diyl] nitrogen chains [-N-N-N=N-]_∞ .