Solid state complex chemistry: formation, structure, and properties of homoleptic tetracyanamidogermanates RbRE[Ge(CN2)4] (RE = La, Pr, Nd, Gd)
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Updated: May 6, 2026

Synthesis of Nine-atom Deltahedral Zintl Ions of Germanium and their Functionalization with Organic Groups
Published on: February 11, 2012
Markus Kalmutzki1, David Enseling, John E C Wren
1Section for Solid State and Theoretical Inorganic Chemistry, Institute of Inorganic Chemistry , Universität Tübingen, Auf der Morgenstelle 18, 72076 Tübingen, Germany.
Abstract:
Tetracyanamidometallates with the general formula RbRE[T(CN2)4] (RE = La, Pr, Nd, Gd; T = Si, Ge) were prepared by solid state metathesis reactions starting from stoichiometric mixtures of RECl3, A2[TF6], and Li2(CN2). Reactions were studied by differential thermal analysis that showed ignition temperatures between 360 and 390 °C for the formation of RbGd[T(CN2)4] with T = Si and Ge. The powder diffraction patterns of RbRE[Ge(CN2)4] were indexed isotypically to the already known RbRE[Si(CN2)4] compound. IR spectra of RbLa[Ge(CN2)4] were measured and compared with those of RbLa[Si(CN2)4]. (73)Ge, (87)Rb, and (139)La solid state NMR measurements and density functional theory calculations were used to verify the novel homoleptic [Ge(CN2)4](4-) ion. Luminescence properties of Eu(3+), Ce(3+), and Tb(3+) doped samples are reported.
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