Structure Determination of Tetranitromethane, C(NO2)4, in the Solid and Gaseous Phases

固相和气相四硝基甲烷 C(NO2)4 的结构测定

• 批准号: 325092365
• 负责人: Professor Dr. Thomas M. Klapötke
• 金额: --
• 依托单位: Department Chemie
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2016
• 资助国家: 德国
• 起止时间: 2015-12-31 至 2017-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/325092365?language=en
• 关键词: Structure; Determination; Tetranitromethane; NO2; Solid

We propose to study the structure of tetranitromethane (C(NO2)4, TNM) in the solid state and the gas phase. TNM is not only a ternary substance, it is the parent molecule for organic nitro materials and thus of fundamental interest. Earlier studies have given partly inconclusive results concerning its structure. In the solid state different phases exist, but the structures have not been solved probably due to molecular dynamics and/or disorder. Earlier vibrational spectroscopy results point to dynamics behaviour in the solid high temperature phase (above -98°C).In the gas phase, two attempts of gas electron diffraction have provided only a partial description of the experimental scattering intensities. A simple description of the experimental results by a quantum-chemically calculated structure of S4 symmetry is not satisfying. We want to circumvent the earlier experimental problem by applying different crystallization techniques in order to gain crystals for X-ray diffraction that lead to resolvable structures in the solid state and to explore the experimental gas phase by new electron diffraction experiments and analysis with a sophisticated dynamic description of the molecules. The preparation of suitable samples will be performed in Munich, the structural chemistry experiments will be carried out in the core facility GED@BI (Centre of Gas Electron Diffraction and Small Molecule Structures) in Bielefeld. The results promise to provide a deeper under¬standing for the reactivity and behaviour of TNM and can be model the understanding of the structure, reactivity and chemical behaviour and their mutual relationships of highly nitrated compounds.

本文研究了四硝基甲烷（C（NO_2）_4，TNM）在固相和气相中的结构。TNM不仅是一种三元物质，它还是有机硝基材料的母体分子，因此具有根本意义。早期的研究给出了关于其结构的部分不确定的结果。在固态中，存在不同的相，但可能由于分子动力学和/或无序，结构尚未解决。早期的振动光谱结果指出了固体高温相（高于-98 ° C）的动力学行为。在气相中，两次气体电子衍射的尝试仅提供了实验散射强度的部分描述。用量子化学计算的S4对称结构来简单描述实验结果是不令人满意的。我们希望通过应用不同的结晶技术来规避早期的实验问题，以便获得用于X射线衍射的晶体，从而在固态下形成可分辨的结构，并通过新的电子衍射实验和分析来探索实验气相，并对分子进行复杂的动态描述。合适样品的制备将在慕尼黑进行，结构化学实验将在比勒费尔德的核心设施GED@BI（气体电子衍射和小分子结构中心）进行。这些结果有望为TNM的反应性和行为提供更深入的理解，并可以为理解高度硝化化合物的结构，反应性和化学行为及其相互关系提供模型。