Pan Fuxing, Wei Shangxin, Guggolz Lukas, Eulenstein Armin R, Tambornino Frank, Dehnen Stefanie
Fachbereich Chemie and Wissenschaftliches Zentrum für Materialwissenschaften, Philipps-Universität Marburg, Hans-Meerwein-Straße 4, 35043 Marburg, Germany.
J Am Chem Soc. 2021 May 12;143(18):7176-7188. doi: 10.1021/jacs.1c02653. Epub 2021 Apr 27.
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.
富含铋的聚阴离子在构建纳米结构铋基材料方面显示出独特的潜力，但对它们的研究仍然很少。我们使用标称组成为“KGaBi”的三元前驱体来形成新型富铋聚阴离子[Bi@Ga(Bi)]（ = 3, 5；在 中）、(GaBi)（在 中）和[{Ru(cod)}Bi]（在 中）的[K(crypt - 222)]盐。它们的铋含量超过了最大的同原子聚阴离子Bi。 和 中阴离子的铋原子数进一步超过了最富铋的二元主族阴离子(GeBi)，并且它们等于（）或超过（）目前报道的具有最多铋原子的阴离子和阳离子[KZnBi]、[(Bi)Ru(Bi)]和[(Bi)Au(Bi)]。化合物 和 是从含有[La(CMeH)]的反应混合物中获得的，[La(CMeH)]显然有助于网络形成但不包含在产物中。在[Ru(cod)(HCC(Me)CH)]存在的情况下，另一条反应途径导致 中阴离子（构象异构体 和 ）的形成，它们是两个“[{Ru(cod)}Bi]”亚基的Bi - Bi连接二聚体。它们包含一个分子内最大的铋原子连接组装体，并且可以被视为通向更大的聚铋化物单元以及最终新的铋变体的过程中的快照。质谱分析使我们能够深入了解簇形成之前溶液中的过程。应用深入的量子化学研究来解释结构特性、观察到的异构体的稳定性以及这些富铋纳米结构的键合特征。这项工作证明了该方法在获取新型铋基材料方面的巨大潜力。
