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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.

Stabilizing a metalloid {Zn12} unit within a polymetallide environment in [K2Zn20Bi16]6−