Zhang Wei-Qiang, Morgan Harry W T, Shu Cong-Cong, McGrady John E, Sun Zhong-Ming
State Key Laboratory of Element-Organic Chemistry, Tianjin Key Lab for Rare Earth Materials and Applications, School of Materials Science and Engineering, Nankai University, Tianjin 300350, China.
Department of Chemistry, University of Oxford, South Parks Road, Oxford OX1 3QR, U.K.
Inorg Chem. 2022 Mar 14;61(10):4421-4427. doi: 10.1021/acs.inorgchem.1c03940. Epub 2022 Mar 1.
The [Nb@As] anion was first isolated from solution in 1986, and a number of isostructural [M@Pn] clusters (M = Nb, Cr, or Mo; Pn = As or Sb; = 2 or 3) have since been reported. We show here how anions of this class can be used as synthetic precursors that, in combination with sources of low-valent late transition metals (Cu and Ag), generate ternary polyarsenide cluster anions with unprecedented structural motifs. Chain type [MM'As] (M = Nb or Ta; M' = Cu or Ag) units are found in compounds . These clusters contain a nortricyclane-like As cage and a [M@As] crown, linked by a single As atom, and represent a fusion of two quite distinct branches of polyarsenide chemistry. Our analysis of the electronic structure confirms that the cluster retains many of the features of the component units. Electrospray ionization mass spectrometry reveals a series of smaller component ions containing 8-12 As atoms, the density functional theory-computed structures of which can be understood in terms of the pseudoelement concept. This work not only presents a new type of coordination mode for As clusters but also offers a point of entry for the rational design of multinary arsenic-based materials.
[Nb@As]阴离子于1986年首次从溶液中分离出来，此后已报道了许多同构的[M@Pn]簇（M = Nb、Cr或Mo；Pn = As或Sb； = 2或3）。我们在此展示了这类阴离子如何用作合成前体，与低价后过渡金属（Cu和Ag）源结合，生成具有前所未有的结构 motif 的三元聚砷化物簇阴离子。在化合物中发现了链状[MM'As]（M = Nb或Ta；M' = Cu或Ag）单元。这些簇包含一个类似降冰片烷的As笼和一个由单个As原子连接的[M@As]冠，代表了聚砷化物化学中两个截然不同分支的融合。我们对电子结构的分析证实，该簇保留了许多组成单元的特征。电喷雾电离质谱揭示了一系列含有8 - 12个As原子的较小组成离子，其密度泛函理论计算结构可根据拟元素概念来理解。这项工作不仅提出了一种新型的As簇配位模式，还为基于多元砷的材料的合理设计提供了切入点。
