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Title: High-Pressure Synthesis of Metal–Inorganic Frameworks Hf4N20·N2, WN8·N2, and Os5N28·3 N2 with Polymeric Nitrogen Linkers

Journal Article · · Angewandte Chemie (International Edition)
ORCiD logo [1];  [2];  [3];  [4];  [5];  [6];  [7];  [7];  [7];  [8];  [2]; ORCiD logo [8];  [9];  [10];  [3]; ORCiD logo [11]; ORCiD logo [4]
  1. Howard Univ., Washington, DC (United States). Dept. of Mathematics; Univ. of Bayreuth (Germany). Bayerisches Geoinstitut; Carnegie Institution for Science, Washington, DC (United States). The Earth and Planets Lab.
  2. Univ. of Chicago, IL (United States). Center for Advanced Radiation Sources
  3. Carnegie Institution for Science, Washington, DC (United States). The Earth and Planets Lab.
  4. Univ. of Bayreuth (Germany). Bayerisches Geoinstitut
  5. Univ. of Bayreuth (Germany). Material Physics and Technology at Extreme Conditions. Lab. of Crystallography
  6. National Univ. of Science and Technology “MISIS”, Moscow (Russian Federation). Materials Modeling and Development Lab.
  7. Linköping Univ. (Sweden). Dept. of Physics, Chemistry and Biology
  8. European Synchrotron Radiation Facility (ESRF), Grenoble (France)
  9. Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany). Photon Science
  10. Howard Univ., Washington, DC (United States). Dept. of Mathematics
  11. Univ. of Bayreuth (Germany). Material Physics and Technology at Extreme Conditions. Lab. of Crystallography; Linköping Univ. (Sweden). Dept. of Physics, Chemistry and Biology
+ Show Author Affiliations

Polynitrides are intrinsically thermodynamically unstable at ambient conditions and require peculiar synthetic approaches. Now, a one-step synthesis of metal–inorganic frameworks Hf4N20·N2, WN8·N2, and Os5N28·3 N2 via direct reactions between elements in a diamond anvil cell at pressures exceeding 100 GPa is reported. The porous frameworks (Hf4N20, WN8, 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 catena-poly[tetraz-1-ene-1,4-diyl] nitrogen chains [–N–N–N=N–]∞.

Research Organization:
Univ. of Chicago, IL (United States); Howard Univ., Washington, DC (United States); Univ. of Bayreuth (Germany); National Univ. of Science and Technology “MISIS”, Moscow (Russian Federation); Linköping Univ. (Sweden)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF); US Army Research Office (ARO); German Research Foundation (DFG); German Federal Ministry of Education and Research (BMBF); Russian Science Foundation; Swedish Government Strategic Research Area in Materials Science on Functional Materials; Knut and Alice Wallenberg Foundation (Sweden); Swedish Research Council (VR)
Grant/Contract Number:
FG02-94ER14466; EAR-1634415; W911NF-19-2-0172; DU 954-11/1; DU 393-9/2; DU 393-13/1; 05K19WC1; 18-12-00492; 2009 00971; KAW-2018.0194; 2019-05600; 2016-05156
OSTI ID:
1646607
Journal Information:
Angewandte Chemie (International Edition), Vol. 59, Issue 26; ISSN 1433-7851
Publisher:
WileyCopyright Statement
Country of Publication:
United States
Language:
English

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Linked Research (4)

Figures / Tables (7)

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