Siladodecahedranes: studies on reactivity, bonding situation, and optoelectronic properties.

硅十二面体：反应性、成键情况和光电性质的研究。

• 批准号: 506550642
• 负责人: Professor Dr. Matthias Wagner
• 金额: --
• 依托单位: Institut für Anorganische und Analytische Chemie
• 依托单位国家: 德国
• 项目类别: Research Grants
• 资助国家: 德国
• 项目状态: 未结题
• 来源: https://gepris.dfg.de/gepris/projekt/506550642?language=en
• 关键词: Siladodecahedranes; studies; reactivity; bonding; situation

We will investigate in detail the experimentally largely unexplored substance class of siladodecahedranes. While numerous theoretical papers document a keen interest in this topic, it was only in 2015 that the anion [Cl@Si32Cl44]‒, the first preparatively accessible siladodecahedrane, was described by our group (27% yield over only one reaction step). Recently, we also published the perhydrogenated ([Cl@Si20H20]‒) and perchlorinated ([Cl@Si20Cl20]‒) siladodecahedranes. For compound analysis, we have optimized mass spectrometric methods and recognized the rarely used 35/37Cl NMR spectroscopy as a powerful tool. Basically, clusters can be modified in three ways: i) surface modification, ii) cluster expansion/contraction by insertion/extrusion reactions, and iii) cluster opening by scaffold-bond cleavage. Since our clusters are a completely new class of materials to be comprehensively investigated, we aim to cover all three areas in this project, with flexibility to adjust the individual weights depending on the results during the course of the project. From this, we derive the following work packages (WP):- WP1: Derivatization of the Si32 framework, starting from [Cl@Si32Cl44]‒, [Cl@Si32H44]‒ and [Cl@Si32H36Me8]‒, in particular by nucleophilic/electrophilic exchange and hydrosilylation reactions.- WP2: Derivatization of the Si20 framework starting from [Cl@Si20Cl20]‒ and [Cl@Si20H20]‒, in particular by nucleophilic/electrophilic exchange and substituent abstractions.- WP3: Investigation of the electronic structure of the (Si)n clusters by NMR spectroscopy, UV-vis and emission spectroscopy on suitable push-pull derivatives, cyclic voltammetry and quantum chemical calculations (cooperation with AK Grimme).- WP4: Modification of the Si20 cluster by insertion of atoms (e.g. O) or reactive molecules (e.g. :CR2) into individual polyhedral edges (cage extension). Cage opening by reductive (e.g. [Cl@Si20H20]‒ using alkali metals) or oxidative (e.g. [[Cl@Si20Cl20]‒ using Cl2) cleavage of individual Si-Si bonds of the cage.

我们将详细研究在实验上基本上未探索的物质类别的硅杂十面体。虽然许多理论论文记录了对这一主题的浓厚兴趣，但直到2015年，我们的小组才描述了阴离子[Cl@Si32Cl44] nH3，这是第一种可通过化学反应获得的硅十二烷（仅一个反应步骤的产率为27%）。最近，我们还发表了全氢化（[Cl@Si20H20] H2O）和全氯化（[Cl@Si20Cl20] H2O）硅杂十面体。对于化合物分析，我们优化了质谱方法，并认识到很少使用的35/37 Cl NMR光谱是一个强大的工具。基本上，簇可以以三种方式修饰：i）表面修饰，ii）通过插入/挤出反应的簇膨胀/收缩，和iii）通过骨架键断裂的簇打开。由于我们的集群是一个全新的材料类别进行全面调查，我们的目标是涵盖所有三个领域在这个项目中，灵活地调整个别权重取决于项目过程中的结果。- WP 1：Si 32骨架的衍生化，从[Cl@Si32Cl44] NH 4、[Cl@Si32H44] NH 4和[Cl@Si32H36Me8] NH 4开始，特别是通过亲核/亲电交换和氢化硅烷化反应。WP 2：从[Cl@Si20Cl20] Cl和[Cl@Si20H20] Cl开始衍生Si 20骨架，特别是通过亲核/亲电交换和取代基提取。工作点3：通过核磁共振光谱、紫外可见光谱和发射光谱对（Si）n簇的电子结构进行研究，适用于推挽衍生物、循环伏安法和量子化学计算（与AK格里姆合作）。WP 4：通过将原子（例如O）或反应性分子（例如CR2）插入到单个多面体边缘（笼状延伸）中来修饰Si 20簇。通过笼的单个Si-Si键的还原性（例如使用碱金属的[Cl@Si20H20]裂解）或氧化性（例如使用Cl 2的[[Cl@Si20Cl20]裂解）裂解来开笼。