Stabilizing a metalloid Zn$_{12}$ unit within a polymetallide environment in [K$_{2}$Zn$_{20}$Bi$_{16}$]$^{6-}$

The access to molecules comprising direct Zn–Zn bonds has become very topical in recent years for various reasons. Low-valent organozinc compounds show remarkable reactivities, and larger Zn–Zn-bonded gas-phase species exhibit a very unusual coexistence of insulating and metallic properties. However, as Zn atoms do not show a high tendency to form clusters in condensed phases, synthetic approaches for generating purely inorganic metalloid Zn$_{x}$ units under ambient conditions have been lacking so far. Here we show that the reaction of a highly reductive solid with the nominal composition K$_{5}$Ga$_{2}$Bi$_{4}$ with ZnPh2 at room temperature yields the heterometallic cluster anion [K$_{2}$Zn$_{20}$Bi$_{16}$]$^{6-}$. A 24-atom polymetallide ring embeds a metalloid {Zn$_{12}$} unit. Density functional theory calculations reveal multicenter bonding, an essentially zero-valent situation in the cluster center, and weak aromaticity. The heterometallic character, the notable electron-delocalization, and the uncommon nano-architecture points at a high potential for nano-heterocatalysis.