Unraveling the Bonding Complexity of Polyhalogen Anions: High-Pressure Synthesis of Unpredicted Sodium Chlorides Na2Cl3 and Na4Cl5 and Bromide Na4Br5

Yuqing Yin; Alena Aslandukova; Nityasagar Jena; Florian Trybel; Igor A Abrikosov; Bjoern Winkler; Saiana Khandarkhaeva; Timofey Fedotenko; Elena Bykova; Dominique Laniel; Maxim Bykov; Andrey Aslandukov; Fariia I Akbar; Konstantin Glazyrin; Gaston Garbarino; Carlotta Giacobbe; Eleanor L Bright; Zhitai Jia; Leonid Dubrovinsky; Natalia Dubrovinskaia

doi:10.1021/jacsau.3c00090

Unraveling the Bonding Complexity of Polyhalogen Anions: High-Pressure Synthesis of Unpredicted Sodium Chlorides Na₂Cl₃ and Na₄Cl₅ and Bromide Na₄Br₅

JACS Au. 2023 Jun 5;3(6):1634-1641. doi: 10.1021/jacsau.3c00090. eCollection 2023 Jun 26.

Authors

Yuqing Yin^{1

2}, Alena Aslandukova³, Nityasagar Jena⁴, Florian Trybel⁴, Igor A Abrikosov⁴, Bjoern Winkler⁵, Saiana Khandarkhaeva³, Timofey Fedotenko⁶, Elena Bykova^{3

7}, Dominique Laniel⁸, Maxim Bykov⁹, Andrey Aslandukov^{1

3}, Fariia I Akbar^{1

3}, Konstantin Glazyrin⁶, Gaston Garbarino¹⁰, Carlotta Giacobbe¹⁰, Eleanor L Bright¹⁰, Zhitai Jia², Leonid Dubrovinsky³, Natalia Dubrovinskaia^{1

4}

Affiliations

¹ Material Physics and Technology at Extreme Conditions, Laboratory of Crystallography, University of Bayreuth, Bayreuth 95440, Germany.
² State Key Laboratory of Crystal Materials, Shandong University, Jinan 250100, China.
³ Bayerisches Geoinstitut, University of Bayreuth, Bayreuth 95440, Germany.
⁴ Department of Physics, Chemistry and Biology (IFM), Linköping University, Linköping SE-581 83, Sweden.
⁵ Institute für Geowissenschaften, Frankfurt University, Altenhöferallee 1, Frankfurt am Main DE-60438, Germany.
⁶ Photon Science, Deutsches Elektronen-Synchrotron DESY, Notkestr. 85, 22607 Hamburg, Germany.
⁷ Earth and Planets Laboratory, Carnegie Institution for Science, 5241 Broad Branch Road, NW, Washington, District of Columbia 20015, United States.
⁸ Centre for Science at Extreme Conditions and School of Physics and Astronomy, University of Edinburgh, Edinburgh EH9 3FD, U.K.
⁹ Institute of Inorganic Chemistry, University of Cologne, Greinstrasse 6, Cologne 50939, Germany.
¹⁰ European Synchrotron Radiation Facility, B.P.220, Grenoble Cedex F-38043, France.

Abstract

The field of polyhalogen chemistry, specifically polyhalogen anions (polyhalides), is rapidly evolving. Here, we present the synthesis of three sodium halides with unpredicted chemical compositions and structures (tP10-Na₂Cl₃, hP18-Na₄Cl₅, and hP18-Na₄Br₅), a series of isostructural cubic cP8-AX₃ halides (NaCl₃, KCl₃, NaBr₃, and KBr₃), and a trigonal potassium chloride (hP24-KCl₃). The high-pressure syntheses were realized at 41-80 GPa in diamond anvil cells laser-heated at about 2000 K. Single-crystal synchrotron X-ray diffraction (XRD) provided the first accurate structural data for the symmetric trichloride Cl₃^- anion in hP24-KCl₃ and revealed the existence of two different types of infinite linear polyhalogen chains, [Cl]_∞^n- and [Br]_∞^n-, in the structures of cP8-AX₃ compounds and in hP18-Na₄Cl₅ and hP18-Na₄Br₅. In Na₄Cl₅ and Na₄Br₅, we found unusually short, likely pressure-stabilized, contacts between sodium cations. Ab initio calculations support the analysis of structures, bonding, and properties of the studied halogenides.