Unraveling the Bonding Complexity of Polyhalogen Anions: High-Pressure Synthesis of Unpredicted Sodium Chlorides Na$_2$Cl$_3$ and Na$_4$Cl$_5$ and Bromide Na$_4$Br$_5$
| Autor: | Yin, Yuqing, Aslandukova, Alena, Jena, Nityasagar, Trybel, Florian, Abrikosov, Igor A., Winkler, Bjoern, Khandarkhaeva, Saiana, Fedotenko, Timofey, Bykova, Elena, Laniel, Dominique, Bykov, Maxim, Aslandukov, Andrii, Akbar, Fariia Iasmin, Glazyrin, Konstantin, Garbarino, Gaston, Giacobbe, Carlotta, Bright, Eleanor L., Jia, Zhitai, Dubrovinsky, Leonid, Dubrovinskaia, Natalia |
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| Jazyk: | angličtina |
| Rok vydání: | 2023 |
| Předmět: | |
| Zdroj: | JACS Au 3(6), 1634 – 1641 (2023). doi:10.1021/jacsau.3c00090 |
| DOI: | 10.3204/pubdb-2023-03829 |
| Popis: | JACS Au 3(6), 1634 – 1641 (2023). doi:10.1021/jacsau.3c00090 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-Na$_2$Cl$_3$, hP18-Na$_4$Cl$_5$, and hP18-Na$_4$Br$_5$), a series of isostructural cubic cP8-AX$_3$ halides (NaCl$_3$, KCl$_3$, NaBr$_3$, and KBr$_3$), and a trigonal potassium chloride (hP24-KCl$_3$). 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–}$, in the structures of cP8-AX$_3$ compounds and in hP18-Na$_4$Cl$_5$ and hP18-Na$_4$Br$_5$. In Na$_4$Cl$_5$ and Na$_4$Br$_5$, 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. Published by ACS Publications, Washington, DC |
| Databáze: | OpenAIRE |
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