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 ZnPh(2) 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.