High-Pressure Synthesis of Metal–Inorganic Frameworks Hf4N20⋅N2, WN8⋅N2, and Os5N28⋅3 N2 with Polymeric Nitrogen Linkers |
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| Authors: | Dr Maxim Bykov Dr Stella Chariton Dr Elena Bykova Saiana Khandarkhaeva Timofey Fedotenko Alena V Ponomareva Johan Tidholm Ferenc Tasnádi Igor A Abrikosov Pavel Sedmak Dr Vitali Prakapenka Michael Hanfland Hanns-Peter Liermann Prof Mohammad Mahmood Dr Alexander F Goncharov Natalia Dubrovinskaia Prof Leonid Dubrovinsky |
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| Institution: | 1. Department of Mathematics, Howard University, 2400 Sixth Street NW, Washington, DC, 20059 USA;2. Center for Advanced Radiation Sources, University of Chicago, 9700 South Cass Avenue, Lemont, IL, 60437 USA;3. The Earth and Planets Laboratory, Carnegie Institution for Science, 5241 Broad Branch Road, NW, Washington, DC, 20015 USA;4. Bayerisches Geoinstitut, University of Bayreuth, Universitätstrasse 30, 95440 Bayreuth, Germany;5. Material Physics and Technology at Extreme Conditions, Laboratory of Crystallography, University of Bayreuth, Universitätstrasse 30, 95440 Bayreuth, Germany;6. Materials Modeling and Development Laboratory, National University of Science and Technology “MISIS”, 119049 Moscow, Russia;7. Department of Physics, Chemistry and Biology (IFM), Linköping University, 58183 Linköping, Sweden;8. European Synchrotron Radiation Facility, BP 220, 38043 Grenoble Cedex, France;9. Photon Science, Deutsches Elektronen-Synchrotron, Notkestrasse 85, 22607 Hamburg, Germany |
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| Abstract: | 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-polytetraz-1-ene-1,4-diyl] nitrogen chains −N−N−N=N−]∞. |
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| Keywords: | high-pressure synthesis inclusion compounds inorganic double helix metal–inorganic frameworks polynitrides |
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