Stabilization Of The CN3 5- Anion In Recoverable High-pressure Ln3 O2 (CN3 ) (Ln=La, Eu, Gd, Tb, Ho, Yb) Oxoguanidinates

Andrey Aslandukov; Pascal L Jurzick; Maxim Bykov; Alena Aslandukova; Artem Chanyshev; Dominique Laniel; Yuqing Yin; Fariia I Akbar; Saiana Khandarkhaeva; Timofey Fedotenko; Konstantin Glazyrin; Stella Chariton; Vitali Prakapenka; Fabrice Wilhelm; Andrei Rogalev; Davide Comboni; Michael Hanfland; Natalia Dubrovinskaia; Leonid Dubrovinsky

doi:10.1002/anie.202311516

Stabilization Of The CN₃ ^5- Anion In Recoverable High-pressure Ln₃ O₂ (CN₃ ) (Ln=La, Eu, Gd, Tb, Ho, Yb) Oxoguanidinates

Angew Chem Int Ed Engl. 2023 Nov 20;62(47):e202311516. doi: 10.1002/anie.202311516. Epub 2023 Oct 16.

Authors

Andrey Aslandukov^{1

2}, Pascal L Jurzick³, Maxim Bykov³, Alena Aslandukova¹, Artem Chanyshev¹, Dominique Laniel⁴, Yuqing Yin², Fariia I Akbar¹, Saiana Khandarkhaeva¹, Timofey Fedotenko⁵, Konstantin Glazyrin⁵, Stella Chariton⁶, Vitali Prakapenka⁶, Fabrice Wilhelm⁷, Andrei Rogalev⁷, Davide Comboni⁷, Michael Hanfland⁷, Natalia Dubrovinskaia^{2

8}, Leonid Dubrovinsky¹

Affiliations

¹ Bayerisches Geoinstitut, University of Bayreuth, Universitätstrasse 30, 95440, Bayreuth, Germany.
² Material Physics and Technology at Extreme Conditions, Laboratory of Crystallography, University of Bayreuth, Universitätstrasse 30, 95440, Bayreuth, Germany.
³ Institute of Inorganic Chemistry, University of Cologne, Greinstrasse 6, 50939, Cologne, Germany.
⁴ Centre for Science at Extreme Conditions and School of Physics and Astronomy, University of Edinburgh, EH9 3FD, Edinburgh, United Kingdom.
⁵ Deutsches Elektronen-Synchrotron DESY, Notkestrasse 85, 22607, Hamburg, Germany.
⁶ Center for Advanced Radiation Sources, University of Chicago, Chicago, Illinois, 60637, USA.
⁷ European Synchrotron Radiation Facility BP 220, 38043, Grenoble Cedex, France.
⁸ Department of Physics, Chemistry and Biology (IFM), Linköping University, SE-581 83, Linköping, Sweden.

PMID: 37768278
DOI: 10.1002/anie.202311516

Abstract

A series of isostructural Ln₃ O₂ (CN₃ ) (Ln=La, Eu, Gd, Tb, Ho, Yb) oxoguanidinates was synthesized under high-pressure (25-54 GPa) high-temperature (2000-3000 K) conditions in laser-heated diamond anvil cells. The crystal structure of this novel class of compounds was determined via synchrotron single-crystal X-ray diffraction (SCXRD) as well as corroborated by X-ray absorption near edge structure (XANES) measurements and density functional theory (DFT) calculations. The Ln₃ O₂ (CN₃ ) solids are composed of the hitherto unknown CN₃ ^5- guanidinate anion-deprotonated guanidine. Changes in unit cell volumes and compressibility of Ln₃ O₂ (CN₃ ) (Ln=La, Eu, Gd, Tb, Ho, Yb) compounds are found to be dictated by the lanthanide contraction phenomenon. Decompression experiments show that Ln₃ O₂ (CN₃ ) compounds are recoverable to ambient conditions. The stabilization of the CN₃ ^5- guanidinate anion at ambient conditions provides new opportunities in inorganic and organic synthetic chemistry.

Keywords: Diamond Anvil Cell; Guanidinate; High Pressure; Lanthanides; Single-Crystal X-Ray Diffraction.

Abstract

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