期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 59, 期 26, 页码 10321-10326出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202002487
关键词
high-pressure synthesis; inclusion compounds; inorganic double helix; metal-inorganic frameworks; polynitrides
资金
- National Science Foundation-Earth Sciences [EAR-1634415]
- Department of Energy-GeoSciences [DE-FG02-94ER14466]
- Army Research Office
- Deutsche Forschungsgemeinschaft (DFG) [DU 95411/1, DU 393-9/2, DU 393-13/1]
- Federal Ministry of Education and Research, Germany (BMBF) [05K19WC1]
- Russian Science Foundation [18-12-00492]
- Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkcping University (Faculty Grant SFO-Mat-LiU) [2009 00971]
- Knut and AliceWallenberg Foundation [KAW-2018.0194]
- Swedish Research Council (VR) [2019-05600]
- VINN Excellence Center Functional Nanoscale Materials (FunMat-2) [2016-05156]
- [W911NF-19-2-0172]
- Russian Science Foundation [18-12-00492] Funding Source: Russian Science Foundation
Polynitrides are intrinsically thermodynamically unstable at ambient conditions and require peculiar synthetic approaches. Now, a one-step synthesis of metal-inorganic frameworks Hf4N20 center dot N2, WN 8 center dot N2, and Os5N28 center dot 3N2 via direct reactions between elements in a diamond anvil cell at pressures exceeding 100 GPa is reported. The porous frameworks (Hf4N20, WN 8, and Os5N28) 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 Hf2N11 that features double-helix catenapoly[tetraz-1-ene-1,4-diyl] nitrogen chains [-N-N-N=N-](infinity.)
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