Stabilizing a metalloid {Zn₁₂} unit within a polymetallide environment in [K₂Zn₂₀Bi₁₆]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 K₅Ga₂Bi₄ with ZnPh₂ at room temperature yields the heterometallic cluster anion [K₂Zn₂₀Bi₁₆]^6-. A 24-atom polymetallide ring embeds a metalloid {Zn₁₂} 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.