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

我们将详细研究在实验上尚未开发的硅十二面体烷类物质。虽然许多理论论文记录了对该主题的浓厚兴趣，但直到2015年，我们的团队才描述了阴离子[Cl@Si32Cl44] -，这是第一个可制备的硅十二面体烷（仅一个反应步骤的产率为27%）。最近，我们还发表了过氢化（[Cl@Si20H20] -）和高氯化（[Cl@Si20Cl20] -）硅十二面体烷。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35/37Cl核磁共振谱是一个强大的工具。基本上，团簇可以通过三种方式进行修饰：i)表面修饰，ii)通过插入/挤压反应进行团簇扩张/收缩，以及iii)通过支架键解理打开团簇。由于我们的集群是一种全新的材料类别，需要进行全面的研究，我们的目标是在这个项目中涵盖所有三个领域，并根据项目过程中的结果灵活地调整单个权重。由此，我们导出了以下工作包（WP）：- WP1: Si32框架的衍生化，从[Cl@Si32Cl44] -， [Cl@Si32H44] -和[Cl@Si32H36Me8] -开始，特别是通过亲核/亲电交换和硅氢化反应。- WP2：从[Cl@Si20Cl20] -和[Cl@Si20H20] -开始的Si20框架衍生化，特别是通过亲核/亲电交换和取代基抽象。- WP3：在合适的推挽衍生物、循环伏安法和量子化学计算上，通过核磁共振光谱、紫外可见光谱和发射光谱研究（Si）n簇的电子结构（与AK Grimme合作）。- WP4：通过将原子（如O）或反应性分子（如CR2）插入到单个多面体边缘（笼形扩展）来修饰Si20簇。通过还原（例如[Cl@Si20H20] -使用碱金属）或氧化（例如[[Cl@Si20Cl20] -使用Cl2）裂解笼的单个Si-Si键来打开笼。

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.