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Aslandukov, Andrii ; Liang, Akun ; Ehn, Amanda ; Trybel, Florian ; Yin, Yuqing ; Aslandukova, Alena ; Akbar, Fariia Iasmin ; Ranieri, Umbertoluca ; Spender, James ; Howie, Ross T. ; Bright, Eleanor Lawrence ; Wright, Jonathan ; Hanfland, Michael ; Garbarino, Gaston ; Mezouar, Mohamed ; Fedotenko, Timofey ; Abrikosov, Igor A. ; Dubrovinskaia, Natalia ; Dubrovinsky, Leonid ; Laniel, Dominique:
Synthesis of LaCN₃, TbCN₃, CeCN5, and TbCN₅ Polycarbonitrides at Megabar Pressures.
In: Journal of the American Chemical Society.
Bd. 146
(2024)
Heft 26
.
- S. 18161-18171.
ISSN 1520-5126
DOI: https://doi.org/10.1021/jacs.4c06068
Volltext
Abstract
Inorganic ternary metal–C–N compounds with covalently bonded C–N anions encompass important classes of solids such as cyanides and carbodiimides, well known at ambient conditions and composed of [CN]− and [CN2]2– anions, as well as the high-pressure formed guanidinates featuring [CN3]5– anion. At still higher pressures, carbon is expected to be 4-fold coordinated by nitrogen atoms, but hitherto, such CN4-built anions are missing. In this study, four polycarbonitride compounds (LaCN3, TbCN3, CeCN5, and TbCN5) are synthesized in laser-heated diamond anvil cells at pressures between 90 and 111 GPa. Synchrotron single-crystal X-ray diffraction (SCXRD) reveals that their crystal structures are built of a previously unobserved anionic single-bonded carbon–nitrogen three-dimensional (3D) framework consisting of CN4 tetrahedra connected via di- or oligo-nitrogen linkers. A crystal-chemical analysis demonstrates that these polycarbonitride compounds have similarities to lanthanide silicon phosphides. Decompression experiments reveal the existence of LaCN3 and CeCN5 compounds over a very large pressure range. Density functional theory (DFT) supports these discoveries and provides further insight into the stability and physical properties of the synthesized compounds.