Multinary, non-oxidic metalates as well as metalides have been actively investigated by many research groups over the past decades, regarding basic properties as well as their potential use as innovative materials.1,2 Recently, binary main group element aggregates proved to be useful synthetic tools for the access of multinary transition metal-main group (semi)metal clusters.3-5 Reactions of binary anions of groups 13-15, [E13/14xE15y]q– (E13/14 = Ga, In, Tl; Ge, Sn, Pb; E15 = P, As, Sb, Bi), with transition metal, lanthanide or actinide compounds lead to the formation of multinary intermetalloid cluster anions.7 Here, (semi)metal cages of p-block elements enclose or incorporate metal atoms of the d- or f-block (M). Clusters like [Ta@Ge8As6]3–, [An@Bi12]q– (An/q = Th/4, U/3), [Au6(Ge3As)(Ge2As2)3]3−, or [K2Zn20Bi16]6–,6-10 might be viewed as molecular models to doped (semi)metals, thereby exhibiting a large variety of unprecedented and unusual geometric and electronic structures, including strong π-aromaticity of [Th@Bi12]4– , (see figure).

“Doping” at the molecular scale: Multinary intermetalloid clusters

ACS Fall 2021

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