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High‐Pressure Synthesis of Metal–Inorganic Frameworks Hf 4 N 20 ⋅N 2 , WN 8 ⋅N 2 , and Os 5 N 28 ⋅3 N 2 with Polymeric Nitrogen Linkers
Author(s) -
Bykov Maxim,
Chariton Stella,
Bykova Elena,
Khandarkhaeva Saiana,
Fedotenko Timofey,
Ponomareva Alena V.,
Tidholm Johan,
Tasnádi Ferenc,
Abrikosov Igor A.,
Sedmak Pavel,
Prakapenka Vitali,
Hanfland Michael,
Liermann HannsPeter,
Mahmood Mohammad,
Goncharov Alexander F.,
Dubrovinskaia Natalia,
Dubrovinsky Leonid
Publication year - 2020
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202002487
Subject(s) - chemistry , polyacetylene , crystallography , metal , transition metal , nitrogen , diamond anvil cell , molecule , high pressure , catalysis , polymer , organic chemistry , thermodynamics , physics
Polynitrides are intrinsically thermodynamically unstable at ambient conditions and require peculiar synthetic approaches. Now, a one‐step synthesis of metal–inorganic frameworks Hf 4 N 20 ⋅N 2 , WN 8 ⋅N 2 , and Os 5 N 28 ⋅3 N 2 via direct reactions between elements in a diamond anvil cell at pressures exceeding 100 GPa is reported. The porous frameworks (Hf 4 N 20 , WN 8 , and Os 5 N 28 ) 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 N 2 also leads to a non‐centrosymmetric polynitride Hf 2 N 11 that features double‐helix catena‐poly[tetraz‐1‐ene‐1,4‐diyl] nitrogen chains [−N−N−N=N−] ∞ .