The encapsulation of actinide ions in intermetalloid clusters has long been proposed but was never realized synthetically. We report the isolation and experimental, as well as quantum chemical, characterization of the uranium-centered clusters [U@Bi12](3-), [U@Tl2Bi11](3-), [U@Pb7Bi7](3-), and [U@Pb4Bi9](3-), upon reaction of (EE'Bi2)(2-) (E = Ga, Tl, E' = Bi; E = E' = Pb) and [U(C5Me4H)3] or [U(C5Me4H)3Cl] in 1,2-diaminoethane. For [U@Bi12](3-), magnetic susceptibility measurements rationalize an unprecedented antiferromagnetic coupling between a magnetic U(4+) site and a unique radical Bi12(7-) shell.

Until now, polycyclic bismuth polyanions have not been known-thus discriminating bismuth from its lighter congeners. However, the synthesis of [K([2.2.2]crypt)]3 (Bi11 )⋅2 py⋅tol, allows us to present the first structurally characterized homoatomic, polycyclic bismuth polyanion, which exhibits the [P11 ](3-) "ufosan" structure. It was obtained upon treatment of [K([2.2.2]crypt)]2 (GaBi3 )⋅en with the solvent pyridine. The binary Zintl anion [GaBi3 ](2-) decomposes under oxidative coupling of pyridine molecules and release of H2 to form the title compound. The unprecedented reaction, its products and by-products were investigated by means of spectroscopy, spectrometry, and DFT studies. All findings reveal the specific reaction conditions to be crucial for the formation of the [Bi11 ](3-) ion-and indicate the possibility of the generation and isolation of further, large bismuth polyanions.

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Bismuth-rich polyanions show a unique potential in constructing nanostructured bismuth-based materials, but they are still poorly investigated. We use a ternary precursor of the nominal composition "K 5 Ga 2 Bi 4 " for the formation of [K(crypt-222)] + salts of novel Bi-rich polyanions [Bi@Ga 8 (Bi 2 ) 6 ] q− (q = 3, 5; in 1), (Ga 2 Bi 16 ) 4− (in 2), and [{Ru(cod)} 4 Bi 18 ] 4− (in 3). Their bismuth contents exceed that of the largest homoatomic polyanion, Bi 11 3− . The numbers of bismuth atoms in the anions in 2 and 3 furthermore surmount that of the Bi-richest binary main-group anion, (Ge 4 Bi 14 ) 4− , and they equal (2) or surmount (3) that reported for the anion and the cations with the largest number of Bi atoms so far, [K 2 Zn 20 Bi 16 ] 6− , [(Bi 8 )Ru(Bi 8 )] 6+ , and [(Bi 8 )Au(Bi 8 )] 5+ . Compounds 1 and 2 were obtained from reaction mixtures that contain [La(C 5 Me 4 H) 3 ], apparently assisting in the network formation without being included in the products. In the presence of [Ru(cod)(H 2 CC(Me)CH 2 ) 2 ], yet another reaction pathway leads to the formation of the anions in 3 (conformers 3a and 3b), which are Bi−Bi linked dimers of two "[{Ru(cod)} 2 Bi 9 ] 2− " subunits. They comprise the largest connected assemblies of Bi atoms within one molecule and may be viewed as snapshots on the way toward even larger polybismuthide units and, ultimately, new bismuth modifications. Mass spectrometry allowed insight into the processes in solution that precede the cluster formation. In-depth quantum chemical studies were applied to explain structural peculiarities, stabilities of the observed isomers, and bonding characteristics of these bismuth-rich nanoarchitectures. The work demonstrates the high potential of the method for the access of new Bi-based materials.

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 Znx 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.