TY - JOUR
T1 - Unraveling the Bonding Complexity of Polyhalogen Anions: High-Pressure Synthesis of Unpredicted Sodium Chlorides Na2Cl3 and Na4Cl5 and Bromide Na4Br5
AU - Yin, Yuqing
AU - Aslandukova, Alena
AU - Jena, Nityasagar
AU - Trybel, Florian
AU - Abrikosov, Igor A.
AU - Winkler, Bjoern
AU - Khandarkhaeva, Saiana
AU - Fedotenko, Timofey
AU - Bykova, Elena
AU - Laniel, Dominique
AU - Bykov, Maxim
AU - Aslandukov, Andrey
AU - Akbar, Fariia I.
AU - Glazyrin, Konstantin
AU - Garbarino, Gaston
AU - Giacobbe, Carlotta
AU - Bright, Eleanor L.
AU - Jia, Zhitai
AU - Dubrovinsky, Leonid
AU - Dubrovinskaia, Natalia
N1 - Funding Information:
The authors acknowledge the Deutsches Elektronen-Synchrotron (DESY, PETRA III) and the European Synchrotron Radiation Facility (ESRF) for provision of beamtime at the P02.2, and ID11 and ID27 beamlines, respectively. Y.Y. acknowledges the financial support provided by the China Scholarship Council (CSC) during her visit to the University of Bayreuth. N.D. and L.D. thank the Federal Ministry of Education and Research, Germany (BMBF, grant no. 05K19WC1), and the Deutsche Forschungsgemeinschaft (DFG; projects DU 954-11/1, DU 393-9/2, and DU 393-13/1) for financial support. N.D. also thanks the Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linköping University (Faculty grant SFO-Mat-LiU no. 2009 00971). M.B. acknowledges the support of Deutsche Forschungsgemeinschaft (DFG Emmy-Noether project BY112/2-1). D.L. thanks the UKRI Future Leaders Fellowship (MR/V025724/1) for financial support. N.J., F.T., and I.A.A. acknowledge support by the Knut and Alice Wallenberg Foundation (Wallenberg Scholar grant no. KAW-2018.0194). Support from the Swedish Research Council (VR) grant no. 2019-05600 and the Swedish Government Strategic Research Areas in Materials Science on Functional Materials at Linköping University (Faculty grant SFO-Mat-LiU no. 2009 00971) is gratefully acknowledged. DFT calculations were enabled by resources provided by the National Academic Infrastructure for Supercomputing in Sweden (NAISS) at National Supercomputer Center partially funded by the Swedish Research Council through grant agreement no. 2022-06725. For the purpose of open access, the author has applied a creative commons attribution (CC BY) license to any author accepted manuscript version arising from this submission.
Publisher Copyright:
© 2023 The Authors. Published by American Chemical Society
PY - 2023/6/26
Y1 - 2023/6/26
N2 - 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.
AB - 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.
KW - alkali halides
KW - halogen bonding
KW - high-pressure chemistry
KW - polyhalogen anions
KW - X-ray diffraction
UR - https://www.scopus.com/pages/publications/85163277759
U2 - 10.1021/jacsau.3c00090
DO - 10.1021/jacsau.3c00090
M3 - Article
AN - SCOPUS:85163277759
SN - 2691-3704
VL - 3
SP - 1634
EP - 1641
JO - JACS Au
JF - JACS Au
IS - 6
ER -