Insights into Formation and Relationship of Multimetallic Clusters: On the Way toward Bi-Rich Nanostructures.

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 "KGaBi" for the formation of [K(crypt-222)] salts of novel Bi-rich polyanions [Bi@Ga(Bi)] ( = 3, 5; in ), (GaBi) (in ), and [{Ru(cod)}Bi] (in ). Their bismuth contents exceed that of the largest homoatomic polyanion, Bi. The numbers of bismuth atoms in the anions in and furthermore surmount that of the Bi-richest binary main-group anion, (GeBi), and they equal () or surmount () that reported for the anion and the cations with the largest number of Bi atoms so far, [KZnBi], [(Bi)Ru(Bi)], and [(Bi)Au(Bi)]. Compounds and were obtained from reaction mixtures that contain [La(CMeH)], apparently assisting in the network formation without being included in the products. In the presence of [Ru(cod)(HCC(Me)CH)], yet another reaction pathway leads to the formation of the anions in (conformers and ), which are Bi-Bi linked dimers of two "[{Ru(cod)}Bi]" 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.