Wilson Robert J, Weigend Florian, Dehnen Stefanie
Fachbereich Chemie and Wissenschaftliches Zentrum für, Materialwissenschaften, Philipps-Universität Marburg, Hans-Meerwein Straße 4, 35043, Marburg, Germany.
Institute of Nanotechnology, Karlsruhe Institute of Technology, Hermann-von-Helmholtz-Platz 1, 76344, Eggenstein-Leopoldshafen, Germany.
Angew Chem Int Ed Engl. 2020 Aug 17;59(34):14251-14255. doi: 10.1002/anie.202002863. Epub 2020 Jul 8.
The pseudo-element concept, in its most general formulation, states that isoelectronic atoms form equal numbers of bonds. Hence, clusters such as Zintl ions usually retain their structure upon isoelectronic replacement of some or all atoms. Here, a deviation from this common observation is presented, namely the formation of (Sn Sb ) (1), a rare example of an eight-vertex Zintl ion, and an unprecedented example of a Zintl ion synthesized by solution means that has an arachno-type structure according to the Wade-Mingos rules. Three structure-types of interest for (Sn Sb ) were identified by DFT calculations: one that matched the X-ray diffraction data, and two that that were reminiscent of fragments of known clusters. A study on the isoelectronic series of clusters, (Sn Sb ) (x=0-8), showed that the relative energies of these three isomers vary significantly with composition (independent of electron count) and that each is the global minimum at least once within the series.
在最一般的表述中,赝元素概念指出等电子原子形成数量相等的键。因此,诸如津特耳离子之类的簇合物在部分或全部原子进行等电子取代后通常会保留其结构。在此,呈现了与这一常见观察结果的偏差,即形成了(SnSb)(1),这是一种罕见的八顶点津特耳离子实例,也是通过溶液法合成的具有前所未有的蛛网型结构的津特耳离子实例,根据韦德 - 明戈斯规则,该结构符合蛛网型结构。通过密度泛函理论(DFT)计算确定了(SnSb)的三种感兴趣的结构类型:一种与X射线衍射数据匹配,另外两种让人联想到已知簇合物的片段。对簇合物等电子系列(SnSb)(x = 0 - 8)的研究表明,这三种异构体的相对能量随组成(与电子数无关)而显著变化,并且在该系列中每种异构体至少有一次是全局能量最低结构。