Syntheses, Structure, Magnetism, and Optical Properties of Lutetium-based Interlanthanide Selenides
Ln{sub 3}LuSe{sub 6} (Ln = La, Ce), {beta}-LnLuSe{sub 3} (Ln = Pr, Nd), and Ln{sub x}Lu{sub 4-x}Se{sub 6} (Ln = Sm, Gd; x = 1.82, 1.87) have been synthesized using a Sb{sub 2}Se{sub 3} flux at 1000 C. Ln{sub 3}LuSe{sub 6} (Ln = La, Ce) adopt the U{sub 3}ScS{sub 6}-type three-dimensional structure, which is constructed from two-dimensional {infinity}{sup 2} [Ln{sub 3}Se{sub 6}]{sup 3-} slabs with the gaps between these slabs filled by octahedrally coordinated Lu{sup 3+} ions. The series of {beta}-LnLuSe{sub 3} (Ln = Pr, Nd) are isotypic with UFeS{sub 3}. Their structures include layers formed from LuSe6 octahedra that are separated by eight-coordinate larger Ln{sup 3+} ions in bicapped trigonal prismatic environments. Sm{sub 1.82}Lu{sub 2.18}Se{sub 6} and Gd{sub 1.87}Lu{sub 2.13}Se{sub 6} crystallize in the disordered F-Ln{sub 2}S{sub 3} type structure with the eight-coordinate bicapped trigonal prismatic Ln(1) ions residing in the one-dimensional channels formed by three different double chains via edge and corner sharing. These double chains are constructed from Ln(2)Se{sub 7} monocapped trigonal prisms, Ln(3)Se{sub 6} octahedra, and Ln(4)S{sub 6} octahedra, respectively. The magnetic susceptibilities of {beta}-PrLuSe{sub 3} and {beta}-NdLuSe{sub 3} follow the Curie-Weiss law. Sm{sub 1.82}Lu{sub 2.18}Se{sub 6} shows van Vleck paramagnetism. Magnetic measurements show that Gd{sub 1.87}Lu{sub 2.13}Se{sub 6} undergoes an antiferromagnetic transition around 4 K. Ce{sub 3}LuSe{sub 6} exhibits ferromagnetic ordering below 5 K. The optical band gaps for La{sub 3}LuSe{sub 6}, Ce{sub 3}LuSe{sub 6}, {beta}- PrLuSe{sub 3}, {beta}-NdLuSe{sub 3}, Sm{sub 1.82}Lu{sub 2.18}Se{sub 6}, and Gd{sub 1.87}Lu{sub 2.13}Se{sub 6} are 1.26, 1.10, 1.56, 1.61, 1.51, and 1.56 eV, respectively.
- Research Organization:
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Sponsoring Organization:
- Chemical Sciences Division
- DOE Contract Number:
- DE-AC02-05CH11231
- OSTI ID:
- 926271
- Report Number(s):
- LBNL-28E; INOCAJ; TRN: US200807%%610
- Journal Information:
- Inorganic Chemistry, Vol. 46, Issue 22; Related Information: Journal Publication Date: 10/09/2007; ISSN 0020-1669
- Country of Publication:
- United States
- Language:
- English
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