Oxidation of [Ge₉{Si(SiMe₃)₃}₃]⁻ with LnI₃ (Ln = Eu, Sm, Yb): Isomerism of Metalloid Germanium Clusters

Abstract

The oxidation of K­[Ge9(Hyp)3] (Hyp = Si­(SiMe3)3) with lanthanide triiodides LnI3 (Ln = Eu, Sm, Yb) leads to the formation of novel clusters with a Ge18-core isolated as a co-crystallizate of Ge*18(Hyp)6 (1a) and Ge18(Hyp)5(Si­(SiMe3)2)­(SiMe3) (1b). Clusters 1a and 1b differ distinctly from the known cluster Ge18(Hyp)6 (A), which has been found earlier in the reaction of K­[Ge9(Hyp)3] with FeCl2 and now identified as an intermediate product in the production of compounds 1a and 1b. These three compounds A, 1a, and 1b are thus structural isomers being the first example of genuine isomerism in metalloid main-group cluster compounds.

Atomically precise M 15 (M = Au/Ag/Cu) alloy nanoclusters: Structural analysis, optical and electrocatalytic CO 2 reduction properties

“…This packing mode was consistent with those of several nanoclusters but differed from the "ABBA" packing mode observed for the Au 13 Cu 2 nanocluster (Fig. S9 in the ESM) [40,51].…”

“…Research on such alloy nanoclusters has attracted increasing attention in previous studies [11,20,28,31,33,[38][39][40][41]. From these studies, a preliminary understanding of the origin of the optical properties of metal nanoclusters is obtained, and theoretical guidance for designing nanoclusters with high photoluminescence quantum yields (PLQYs) is provided [4,40,42,43].…”

“…Research on such alloy nanoclusters has attracted increasing attention in previous studies [11,20,28,31,33,[38][39][40][41]. From these studies, a preliminary understanding of the origin of the optical properties of metal nanoclusters is obtained, and theoretical guidance for designing nanoclusters with high photoluminescence quantum yields (PLQYs) is provided [4,40,42,43]. For example, the luminescence of metal nanoclusters primarily originates from their metal cores, and the free electron shrinkage induced by doping with inert metals can significantly increase the PLQY of nanoclusters [26].…”

Oxidative Coupling of [Ge9(Si(SiMe3)3)2]2– with f Elements

“…Compound 1 crystallizes in the orthorhombic space group Pbcn and consists of the dianionic cluster [Ge 18 (Hyp) 4 ] 2– (Figure ) and the [Yb­(thf) 6 ] 2+ counterion (both structures with counterions are shown in the Supporting Information). In contrast to the known neutral metalloid Ge 18 clusters, , the dianion [Ge 18 (Hyp) 4 ] 2– contains two intact Ge 9 cages, which are connected by a single Ge–Ge bond with a length of 244.7 pm. Complex 2 crystallizes in the monoclinic space group P 2 1 / n and shows the same basic structure of [Ge 18 (Hyp) 4 ] 2– (Figure ).…”

“…For the first time, it was oxidized with FeCl 2 in the presence of diphenylphosphinoethane (dppe), resulting in a neutral Ge 18 (Hyp) 6 cluster, which was isolated with very low yield and a reduced Fe­(I) salt [Fe­(dppe)]­[Ge 9 (Hyp) 3 ] was found . Very recently, we found three Ge 18 clusters arising from the oxidation of K­[Ge 9 (Hyp) 3 ] with lanthanide triiodides LnI 3 (Ln = Eu, Sm, Yb), while lanthanides were reduced to the corresponding diiodides LnI 2 . Thus, lanthanide triiodides LnI 3 have proven to be mild oxidizers of metalloid germanium clusters.…”