High-Pressure Synthesis of Nitrogen-Rich Y(N5)3<middle dot>N2 Pentazolate with Perovskite TopologyShow others and affiliations
2025 (English)In: Angewandte Chemie International Edition, ISSN 1433-7851, E-ISSN 1521-3773, Vol. 64, no 31, article id e202506334Article in journal (Refereed) Published
Abstract [en]
The discovery and stabilization of the cyclo-N5(-) anion have introduced a class of pentazolate compounds with significant potential as high-energy-density materials (HEDMs). This potential could be further enhanced by increasing the pentazolate-to-metal ratio. Here, we report the high-pressure, high-temperature synthesis and characterization of a novel yttrium pentazolate, Y(N5)3<middle dot>N2, which exhibits an exceptionally high nitrogen-to-metal ratio of 17:1. Y(N5)3<middle dot>N2 was synthesized from yttrium and nitrogen by laser heating to 3000 K at 125 GPa in a diamond anvil cell. Its crystal structure, a 3D nitrogen-inclusion metal-pentazolate framework, was solved and refined in situ using synchrotron single-crystal X-ray diffraction. This structure demonstrates a perovskite topology, as pentazolate ring centers form octahedra connected via vertices, neutral nitrogen dimers are located at the centers of the octahedra, and yttrium atoms occupy distorted cuboctahedra within the octahedral 3D framework. Density functional theory (DFT) calculations corroborate the experimental findings and provide further insights into the stability and properties of the synthesized compound. Y(N5)3<middle dot>N2 is the first example of stabilizing three pentazolate anions per metal cation, surpassing the previously achieved 1:1 ratio. Additionally, we propose a centroid-based structure typification for solvent-free inorganic pentazolates, serving as an important step for further structural classification of pentazolates and other polynitrides.
Place, publisher, year, edition, pages
WILEY-V C H VERLAG GMBH , 2025. Vol. 64, no 31, article id e202506334
Keywords [en]
Diamond anvil cell; High-pressure; Pentazolate; Single-crystal X-ray diffraction
National Category
Materials Chemistry
Identifiers
URN: urn:nbn:se:liu:diva-215360DOI: 10.1002/anie.202506334ISI: 001508690200001PubMedID: 40384618Scopus ID: 2-s2.0-105008415017OAI: oai:DiVA.org:liu-215360DiVA, id: diva2:1975328
Note
Funding Agencies|Knut and Alice Wallenberg Foundation [KAW-2018.0194]; Deutsche Forschungsgemeinschaft (DFG) [BY112/2-1, DU 954-11/1, DU 945/15-1]; European Union (ERC) [101077963]; Loewe Starting Professorship Program of the State of Hessen and Johanna Quandt Young Academy; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University [2009 00971]; Projekt DEAL
2025-06-242025-06-242025-10-14Bibliographically approved