The accessibility of triads with deltahedral Zintl clusters in analogy to fullerene-linker-fullerene triads is another example for the close relationship between fullerenes and Zintl clusters. The compound {[K(2.2.2-crypt)]4[RGe9-CH=CH-CH=CH-Ge9R]}(toluene)2 (R=(2Z,4E)-7-amino-5-aza-hepta-2,4-dien-2-yl), containing two deltahedral [Ge9] clusters linked by a conjugated (1Z,3Z)-buta-1,3-dien-1,4-diyl bridge, was synthesized through the reaction of 1,4-bis(trimethylsilyl)butadiyne with K4Ge9 in ethylenediamine and crystallized after the addition of 2.2.2-cryptand and toluene. The compound was characterized by single-crystal structure analysis as well asNMR and IR spectroscopy.
[Ge9](4-) Zintl clusters are used as soluble germanium source for a bottom-up fabrication of Ge nanomorphologies such as inverse opal structures with tunable composition. The method is based on the assembly and oxidation of [Ge9 ](4-) clusters in a template mold using SiCl4 , GeCl4 , and PCl3 leading to Si and P-containing Ge phases as shown by X-ray diffraction, Raman spectroscopy, and energy-dispersive X-ray analysis. [Ge9](4-) clusters are retained using ethylenediamine (en) as a transfer medium to a mold after removal of the solvent if water is thoroughly excluded, but are oxidized to amorphous Ge in presence of water traces. (1)H NMR spectroscopy reveals the oxidative deprotonation of en by [Ge9](4-). Subsequent annealing leads to crystalline Ge. As an example for wet-chemical synthesis of complex Ge nanomorphologies, we describe the fabrication of undoped and P-doped inverse opal-structured Ge films with a rather low oxygen contents. The morphology of the films with regular volume porosity is characterized by SEM, TEM, and grazing incidence small-angle X-ray scattering.
The addition of Sn and Zn ions to [Ge ] clusters by reaction of [Ge ] with SnPh Cl , ZnCp* (Cp*=pentamethylcyclopentadienyl), or Zn [HC(Ph P=NPh) ] is reported. The resulting Sn- and Zn-bridged clusters [(Ge )M(Ge )] (M=Sn, q=4; M=Zn, q=6) display various coordination modes. The M atoms that coordinate to the open square of a C -symmetric [Ge ] cluster form strong covalent multicenter M-Ge bonds, in contrast to the M atoms coordinating to triangular cluster faces. Molecular orbital analyses show that the M atoms of the Ge M fragments coordinate to a second [Ge ] cluster with similar orbitals but in different ways. The [Ge Sn] unit donates two electrons to the triangular face of a second [Ge ] cluster with D symmetry, whereas [Ge Zn] acts as an electron acceptor when interacting with the triangular face of a D -symmetric [Ge ] unit.
The first [Ge10](2-) Zintl anion, which is neither filled nor connected to another metal atom is presented in terms of X-ray structure, Raman-spectrum and ESI-MS. Pure [Ge10](2-), adapting a D4d symmetric closo-structure, were crystallized from a Rb4Ge9/ethylendiamine solution, containing 7-amino-1-trimethylsilyl-5-aza-hepta-3-en-1-yne. The role of the latter on the formation of [Rb(222-crypt)]2[Ge10](en)1.5 is discussed.
The accessibility of triads with deltahedral Zintl clusters in analogy to fullerene–linker–fullerene triads is another example for the close relationship between fullerenes and Zintl clusters. The compound {[K(2.2.2‐crypt)]4[RGe9‐CHCHCHCH‐Ge9R]}(toluene)2 (R=(2Z,4E)‐7‐amino‐5‐aza‐hepta‐2,4‐dien‐2‐yl), containing two deltahedral [Ge9] clusters linked by a conjugated (1Z,3Z)‐buta‐1,3‐dien‐1,4‐diyl bridge, was synthesized through the reaction of 1,4‐bis(trimethylsilyl)butadiyne with K4Ge9 in ethylenediamine and crystallized after the addition of 2.2.2‐cryptand and toluene. The compound was characterized by single‐crystal structure analysis as well asNMR and IR spectroscopy.
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