The introduction of the so called fluorolytic sol‐gel synthesis in 2003 gave access to previously inaccessible aluminum oxo‐fluorides, thus to nanoscopic materials and, more importantly, novel catalysts. The intermediate cluster structures synthesized and stabilized by Kemnitz and coworkers have mainly been protected by iso‐propoxide groups. However, since catalytic reactions take place in a large variety of media, hydrophilic analogs of those clusters would be of interest. In this manuscript, we present a computational analysis for the fluorination reaction, which represents the second part of fluorolytic sol‐gel synthesis, and a theoretical study of the synthesized Al4F4(μ4‐O)(μ‐OiPr)5[H(OiPr)2] nanostructure's conversion to its hydroxylated analog Al4F4(μ4‐O)(μ‐OH)5[H(OH)2] utilizing the nudged elastic band method. Furthermore, the role of the fluorine atoms of the cluster in an aqueous medium is evaluated by studying the incremental addition of water molecules to the cluster with and without fluorine atoms. In addition, NMR shifts of clusters exhibiting different substituents are compared. It has been found that the inclusion of an explicit solvent is necessary to capture the magnetic response of the individual cluster atoms in an aqueous solvent correctly. © 2018 Wiley Periodicals, Inc.

中文翻译：

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氟氧化铝簇：稳定性、合成考虑和与水相互作用的第一原理研究

2003 年引入了所谓的氟解溶胶-凝胶合成，从而获得了以前无法获得的氧氟化铝，从而获得了纳米材料，更重要的是，获得了新型催化剂。Kemnitz 及其同事合成和稳定的中间簇结构主要受异丙氧基保护。然而，由于催化反应发生在多种介质中，这些簇的亲水类似物将是令人感兴趣的。在本手稿中，我们对氟化反应进行了计算分析，这代表了氟解溶胶-凝胶合成的第二部分，以及合成的 Al4F4(μ4-O)(μ-OiPr)5[H(OiPr) 2] 利用轻推弹力带法将纳米结构转化为其羟基化类似物 Al4F4(μ4-O)(μ-OH)5[H(OH)2]。此外，团簇的氟原子在水性介质中的作用是通过研究水分子向含氟原子和不含氟原子的团簇的增量添加来评估的。此外，比较了具有不同取代基的簇的 NMR 位移。已经发现，包含显式溶剂对于正确捕获水性溶剂中单个簇原子的磁响应是必要的。© 2018 Wiley Periodicals, Inc. 已经发现，包含显式溶剂对于正确捕获水性溶剂中单个簇原子的磁响应是必要的。© 2018 Wiley Periodicals, Inc. 已经发现，包含显式溶剂对于正确捕获水性溶剂中单个簇原子的磁响应是必要的。© 2018 Wiley Periodicals, Inc.