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High-Pressure Synthesis of Metal-Inorganic Frameworks Hf4 N20 ?N2 , WN8 ?N2 , and Os5 N28 ?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-]? .

SUBMITTER: Bykov M 

PROVIDER: S-EPMC7317814 | biostudies-literature | 2020 Jun

REPOSITORIES: biostudies-literature

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High-Pressure Synthesis of Metal-Inorganic Frameworks Hf<sub>4</sub> N<sub>20</sub> ⋅N<sub>2</sub> , WN<sub>8</sub> ⋅N<sub>2</sub> , and Os<sub>5</sub> N<sub>28</sub> ⋅3 N<sub>2</sub> with Polymeric Nitrogen Linkers.

Bykov Maxim M   Chariton Stella S   Bykova Elena E   Khandarkhaeva Saiana S   Fedotenko Timofey T   Ponomareva Alena V AV   Tidholm Johan J   Tasnádi Ferenc F   Abrikosov Igor A IA   Sedmak Pavel P   Prakapenka Vitali V   Hanfland Michael M   Liermann Hanns-Peter HP   Mahmood Mohammad M   Goncharov Alexander F AF   Dubrovinskaia Natalia N   Dubrovinsky Leonid L  

Angewandte Chemie (International ed. in English) 20200508 26

Polynitrides are intrinsically thermodynamically unstable at ambient conditions and require peculiar synthetic approaches. Now, a one-step synthesis of metal-inorganic frameworks Hf<sub>4</sub> N<sub>20</sub> ⋅N<sub>2</sub> , WN<sub>8</sub> ⋅N<sub>2</sub> , and Os<sub>5</sub> N<sub>28</sub> ⋅3 N<sub>2</sub> via direct reactions between elements in a diamond anvil cell at pressures exceeding 100 GPa is reported. The porous frameworks (Hf<sub>4</sub> N<sub>20</sub> , WN<sub>8</sub> , and Os<sub>5<  ...[more]

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