Syntheses, Structure, Magnetism, and Optical Properties of the Partial Ordered Quaternary Interlanthanide Sulfides PrLnYb2S6 (Ln = Tb, Dy)

Abstract

Dark red single crystals of PrLnYb{sub 2}S{sub 6} (Ln = Pr/Yb, Tb, Dy) have been synthesized through the reaction of elemental rare earth metals and S using a Sb{sub 2}S{sub 3} flux at 1000 C. These isotypic compounds adopt the F-Ln{sub 2}S3 three-dimensional open channel structure type. Eight-coordinate Pr{sup 3+} ions sit in the channels, which are constructed from three different edge-shared double chains running down the b axis, which contain Yb(1)S{sub 6} octahedra, Yb(2)S{sub 6}, octahedra and LnS{sub 7} monocapped trigonal prisms, respectively. Each double chain connects to four other neighbors by sharing vertices and edges. Considerable disordering in Ln positions was observed in single X-ray diffraction experiments only in the case of Pr/Yb. Least square refinements gave rise to the formulas of Pr{sub 1.34}Yb{sub 2.66}S{sub 6}, of PrTbYb{sub 2}S{sub 6}, and PrDyYb{sub 2}S{sub 6}, which are confirmed by the elemental analysis and magnetic susceptibility measurements. Pr1.34Yb2.66S{sub 6}, PrTbYb{sub 2}S{sub 6} and PrDyYb{sub 2}S{sub 6} are paramagnetic down to 2 K without any indications of long range magnetic ordering. The optical transitions for Pr{sub 1.34}Yb{sub 2.66}S{sub 6}, PrTbYb{sub 2}S{sub 6}, and PrDyYb{sub 2}S{sub 6} are at approximately 1.6 eV. Crystallographic data: Pr{sub 1.34}Yb{sub 2.66}S{sub 6}, monoclinic, space group P2{sub 1}/m, a = 10.960(2), b = 3.9501(8), c = 11.220(2) {angstrom}, {beta} = 108.545(3), V = 460.54(16), Z = 2; PrTbYb{sub 2}S{sub 6}, monoclinic, space group P2{sub 1}/m, a = 10.9496(10), b = 3.9429(4), c = 11.2206(10) {angstrom}, {beta} = 108.525(2), V = 459.33(7), Z = 2; PrDyYb{sub 2}S{sub 6}, monoclinic, space group P2{sub 1}/m, a = 10.9384(10), b = 3.9398(4), c = 11.2037(10) {angstrom}, {beta} = 108.612(2), V = 457.57(7), Z = 2

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