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One-Dimensional Quaternary and Penternary Alkali Rare Earth Thiophosphates Obtained via Alkali Halide Flux Crystal Growth

Journal Article · · Crystal Growth and Design
 [1];  [2];  [2];  [2]
  1. Univ. of South Carolina, Columbia, SC (United States); University of South Carolina
  2. Univ. of South Carolina, Columbia, SC (United States)
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Single crystals of nine new quaternary and penternary rare earth containing thiophosphates, Cs2KLn(PS4)2, Rb3-xNaxLn(PS4)2 (Ln = La, Nd), Rb2NaNd(PS4)2, Cs3La(PS4)2, Rb3Gd(PS4)2, and Cs5NaLn2(PS4)4 (Ln = Gd, Tb), were grown in alkali halide eutectic fluxes. All title compounds were structurally characterized by single crystal X-ray diffraction and were found to crystallize in pseudo-one-dimensional structure types, reminiscent of those found for other known alkali rare earth thiophosphates, in a variety of space groups including monoclinic P21/c, P21/m, P21, and orthorhombic Ccca. The crystal structures of the reported compounds are characterized by the formation of complex one-dimensional [(Ln(PS4)2)3–] and [(Ln2(PS4)4)6–] anionic chains that run along the crystallographic α-axis in Cs2KLn(PS4)2, Rb3-xNaxLn(PS4)2 (Ln = La, Nd) and Rb2NaNd(PS4)2, b-axis in Cs3La(PS4)2 and Rb3Gd(PS4)2, and c-axis in Cs5NaLn2(PS4)4 (Ln = Gd, Tb). Cs2KLn(PS4)2, Rb3-xNaxLn(PS4)2 (Ln = La, Nd), Rb2NaNd(PS4)2, Rb3Gd(PS4)2, and Cs3La(PS4)2 feature two crystallographically unique thiophosphate tetrahedra that face- and edge-share with the LnSx polyhedra forming infinite one-dimensional zigzag-like chains. This unusual face-sharing or face-grafting coordination mode of the thiophosphate group is however absent in Cs5NaLn2(PS4)4 (Ln = Gd, Tb), which exhibit only one unique phosphorus site. The magnetic susceptibility and the field-dependent magnetization were measured for Rb2NaNd(PS4)2 and Cs2KNd(PS4)2 which were found to be paramagnetic over the entire 2–300 K temperature range. Finally, optical properties of Cs2KNd(PS4)2 and Rb2.65Na0.35La(PS4)2 were measured by UV–vis diffuse reflectance spectrometry which revealed numerous weak absorption bands in the 300–900 nm range characteristic of the f–f electronic transitions in Nd3+; Rb2.65Na0.35La(PS4)2 was found to be a semiconductor with a direct band gap of 3.60 eV.
Research Organization:
Univ. of South Carolina, Columbia, SC (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0018739
OSTI ID:
1605391
Alternate ID(s):
OSTI ID: 1775431
Journal Information:
Crystal Growth and Design, Journal Name: Crystal Growth and Design Journal Issue: 10 Vol. 19; ISSN 1528-7483
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Crystal structure
Crystallization
Fluxes
Halogens
Inorganic compounds