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

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

Abstract / Description of output

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.

Original languageEnglish
Pages (from-to)1634-1641
Number of pages8
JournalJACS Au
Volume3
Issue number6
Early online date5 Jun 2023
DOIs
Publication statusPublished - 26 Jun 2023

Keywords / Materials (for Non-textual outputs)

  • alkali halides
  • halogen bonding
  • high-pressure chemistry
  • polyhalogen anions
  • X-ray diffraction

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