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American Chemical Society, Inorganic Chemistry, 7(52), p. 3611-3619, 2013

DOI: 10.1021/ic301442f

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Cs_{7}Nd_{11}(SeO_{3})_{12}Cl_{16} : first noncentrosymmetric structure among alkaline-metal lanthanide selenite halides

Journal article published in 2013 by Peter S. Berdonosov, Lev Akselrud, Yurii Prots, Artem M. Abakumov, Philippe F. Smet ORCID, Dirk Poelman ORCID, van Gustaaf Tendeloo, Valery A. Dolgikh
This paper is available in a repository.
This paper is available in a repository.

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Abstract

Cs 7 Nd 11 (SeO 3) 12 Cl 16 , the complex selenite chloride of cesium and neodymium, was synthesized in the NdOCl−SeO 2 −CsCl system. The compound has been characterized using single-crystal X-ray diffraction, electron diffraction, transmission electron microscopy, luminescence spectroscopy, and second-harmonic-generation techniques. Cs 7 Nd 11 (SeO 3) 12 Cl 16 crystallizes in an orthorhombic unit cell with a = 15.911(1) Å, b = 15.951(1) Å, and c = 25.860(1) Å and a noncentrosymmetric space group Pna2 1 (No. 33). The crystal structure of Cs 7 Nd 11 (SeO 3) 12 Cl 16 can be represented as a stacking of Nd 11 (SeO 3) 12 lamellas and CsCl-like layers. Because of the layered nature of the Cs 7 Nd 11 (SeO 3) 12 Cl 16 structure, it features numerous planar defects originating from occasionally missing the CsCl-like layer and violating the perfect stacking of the Nd 11 (SeO 3) 12 lamellas. Cs 7 Nd 11 (SeO 3) 12 Cl 16 represents the first example of a noncentrosymmetric structure among alkaline-metal lanthanide selenite halides. Cs 7 Nd 11 (SeO 3) 12 Cl 16 demonstrates luminescence emission in the near-IR region with reduced efficiency due to a high concentration of Nd 3+ ions causing nonradiative cross-relaxation.