Two new ternary lanthanide antimony chalcogenides: Yb{sub 4}Sb{sub 2}S{sub 11.25} and Tm{sub 4}Sb{sub 2}Se{sub 11.68} containing chalcogenide Q{sup 2-} and dichalcogenide (Q{sub 2}){sup 2-} anions

Journal Article · Thu Mar 15 04:00:00 EDT 2012 · Journal of Solid State Chemistry

DOI:https://doi.org/10.1016/J.JSSC.2012.01.020· OSTI ID:22012070

Babo, Jean-Marie ^[1]

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1. Department of Civil Engineering and Geological Sciences and Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, IN 46556 (United States)

Dark red and dark brown crystals of Yb{sub 4}Sb{sub 2}S{sub 11.25} and Tm{sub 8}Sb{sub 4}Se{sub 11.68}, respectively, were obtained from the reaction of the elements in Sb{sub 2}Q{sub 3} (Q=S, Se) fluxes. Both non-stoichiometric compounds are orthorhombic and crystallize in the same space group Pnnm, with two formula units per unit cell (a=12.446(2), b=5.341(1), c=12.058(2) for sulfide and a=13.126(2), b=5.623(1), c=12.499(2) for the selenide). Their crystal structures are dominated by lanthanide-chalcogenide polyhedra (CN=7 and 8), which share corners, edges, triangular- and square-faces to form a three-dimensional framework embedding antinomy cations. The latter are coordinated by three sulfide anions with 5(1+2+2) secondary contacts forming basically infinite chains running along [0 1 0]. The chalcogens in both compounds form chalcogenide Q{sup 2-} and dichalcogenide (Q{sub 2}){sup 2-} anionic units. The optical analysis made on those compounds shows that both are semiconductors with band gap of 1.71 and 1.22 eV for Yb{sub 4}Sb{sub 2}S{sub 11.25} and Tm{sub 4}Sb{sub 2}Se{sub 11.75,} respectively. - Graphical Abstract: The crystal structure of Yb{sub 4}Sb{sub 2}S{sub 11} viewed along the [0 1 0]. Highlights: Black-Right-Pointing-Pointer Lanthanide chalcogenides. Black-Right-Pointing-Pointer Semiconductors. Black-Right-Pointing-Pointer Tunnel structures. Black-Right-Pointing-Pointer Lone-pair effects.

• OSTI ID: 22012070
• Journal Information: Journal of Solid State Chemistry, Journal Name: Journal of Solid State Chemistry Vol. . 187; ISSN 0022-4596; ISSN JSSCBI
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
ANIONS
ANTIMONY
CARBON NITRIDES
CATIONS
CRYSTALS
FLUX SYNTHESIS
ORTHORHOMBIC LATTICES
RARE EARTHS
SEMICONDUCTOR MATERIALS
SPACE GROUPS
SULFIDES
TUNNELS