Peters Bertram, Stuhrmann Gina, Mack Fabian, Weigend Florian, Dehnen Stefanie
Fachbereich Chemie and Wissenschaftliches Zentrum für Materialwissenschaften, Philipps-Universität Marburg, Hans-Meerwein-Straße 4, 35043, Marburg, Germany.
Institut für Physikalische Chemie, Karlsruher Institut für Technologie (KIT), Kaiserstr. 12, 76131, Karlsruhe, Germany.
Angew Chem Int Ed Engl. 2021 Aug 2;60(32):17622-17628. doi: 10.1002/anie.202104867. Epub 2021 Jun 30.
Supertetrahedral clusters have been reported in two generally different types so far: one type possessing an organic ligand shell, no or low charges, and high solubility, while the other cluster type is ligand-free with usually high charges and low or no solubility in common solvents. The latter is a tremendous disadvantage regarding further use of the clusters in solution. However, as organic substituents usually broaden the HOMO-LUMO gaps, which cannot be overcompensated by the (limited) cluster sizes, a full organic shielding comes along with drawbacks regarding opto-electronic properties. We therefore sought to find a way of generating soluble clusters with a minimum number of organic substituents. Here, we present the synthesis and full characterization of two salts of [Sn O S (SBu) ] that are high soluble in CH Cl or CH CN, which includes first NMR and mass spectra obtained from solutions of such salts with mostly inorganic supertetrahedral clusters. The optical absorption properties of this new class of compounds indicates nearly unaffected band gaps. The synthetic approach and the spectroscopic findings were rationalized and explained by means of high-level quantum chemical studies.
到目前为止，超四面体簇已被报道为两种大致不同的类型：一种类型具有有机配体壳层，电荷为零或较低，且溶解度高，而另一种簇类型不含配体，通常电荷较高，在常见溶剂中的溶解度较低或不溶。对于这些簇在溶液中的进一步应用而言，后者是一个巨大的缺点。然而，由于有机取代基通常会拓宽HOMO-LUMO能隙，而（有限的）簇尺寸无法完全补偿这种拓宽，因此完全的有机屏蔽会带来光电子性质方面的缺点。因此，我们试图找到一种方法来生成具有最少有机取代基数量的可溶性簇。在此，我们展示了两种[Sn O S (SBu) ]盐的合成及全面表征，它们在CH Cl或CH CN中具有高溶解度，这包括首次从这类主要含有无机超四面体簇的盐溶液中获得的核磁共振谱和质谱。这类新化合物的光吸收性质表明其带隙几乎未受影响。通过高水平量子化学研究对合成方法和光谱学发现进行了合理化解释。
