Structure and bonding in Yb4MgGe4: Yb2+/Yb3+ mixed-valency and charge separation

Journal of the American Chemical Society
Paul H Tobash, Svilen Bobev

Abstract

Reported are the synthesis and the structural characterization of a new derivative of the RE5Tt4 family (RE = Rare-earth; Tt = Tetrel, = Si, Ge, i.e., group 14 element), Yb5-xMgxGe4 (x approximately 1). Crystal data for Yb4.04(1)Mg0.96(1)Ge4 at 23 degrees C: orthorhombic, space group Pnma (No. 62), Z = 4; a = 7.155(2) A, b = 14.769(5) A, c = 7.688(2) A; V = 812.5(4) A3. This phase is an example of a substitution of lanthanide metal (Yb) with a nonmagnetic element (Mg) within this structure type. Its structure can alternatively be described as an intergrowth of the hypothetical Yb2MgGe2, which features flat infinite [MgGe2]4- layers and the hypothetical YbGe with [Ge2]6- dimers. The flat [MgGe2]4- layers propagate in two dimensions (a and c), and they are offset by a distance of 1/4.a with respect to one another and are interspaced with layers of [Ge2]6- dimers and Yb cations filling the space between them. According to the structural and physical property data, Yb4MgGe4 is a heterogeneous mixed-valent compound, i.e. a system where one of the two symmetry-inequivalent Yb sites has atoms in closed-shell Yb2+ configuration, whereas the Yb3+ cations occupy a different crystallographic site.

References

Dec 5, 2003·Journal of the American Chemical Society·Yurij MozharivskyjGordon J Miller
Jan 6, 2005·Journal of the American Chemical Society·Yurij MozharivskyjGordon J Miller

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Citations

Dec 8, 2011·Inorganic Chemistry·Svilen BobevJohnpierre Paglione
Mar 10, 2011·Dalton Transactions : an International Journal of Inorganic Chemistry·Jinlei YaoYurij Mozharivskyj
Feb 5, 2015·Angewandte Chemie·F Weinhold, Roger A Klein
Jan 4, 2013·Acta Crystallographica. Section C, Crystal Structure Communications·Nian-Tzu SuenSvilen Bobev
Sep 6, 2012·Dalton Transactions : an International Journal of Inorganic Chemistry·Tae-Soo YouSvilen Bobev
Sep 28, 2010·Physical Review Letters·Y MudrykG J Miller
Apr 21, 2007·The Journal of Physical Chemistry. B·G BalducciM Pani
Mar 14, 2007·Journal of the American Chemical Society·Sheng-qing Xia, Svilen Bobev

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