Czech-German Cooperation Project: Structure studies on inner and outer functionalized icosahedral and bicapped square-antiprismatic boron clusters

捷德合作项目：内外功能化二十面体和双帽方反棱柱硼团簇的结构研究

• 批准号: 234021884
• 负责人: Professor Dr. Norbert W. Mitzel
• 金额: --
• 依托单位: Institute of Inorganic Chemistry
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2013
• 资助国家: 德国
• 起止时间: 2012-12-31 至 2014-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/234021884?language=en
• 关键词: Czech; German; Cooperation; Project; Structure

This is an application for a joint Czech/German collaboration project. The Czech part has been submitted to Czech Science Foundation by Dr. Drahomir Hnyk, Institute of Inorganic Chemistry of the Academy of Science of the Czech Republic. The project aims at the structure determination of functionalized carbaborane-cluster molecules, namely functionalized dicarba-closo-decaboranes (1,2-C2B8H10) and 1,2-dicarba-closo-dodecaborane (1,2-C2B10H12) with some of the terminal hydrogen atoms substituted by EH units (where E = S, Se, Te). These compounds will be used by the Prague group as architecturally rigid building blocks as parts of self assembled monolayer (SAM) based materials. The knowledge of structural data of the underlying molecules is of importance for the application of these compounds in this area. The determination of molecular structures of such boron-cluster molecules by the standard method of structural chemistry, X-ray diffraction (XRD), is often difficult due to limited crystallization ability of the compounds. Therefore we want to apply gas electron diffraction (GED) for this purpose and study the unperturbed structure of the molecules in the gaseous state. The Bielefeld group is one of a few centers worldwide running equipment for GED. Besides pure structure determination, these compounds are ideal candidates for further development of new strategies in GED data analysis. This will also be part of this project. These developments aim at higher precision, reliability and reproducibility of the structural data. This new refinement strategy, introduced by Dr. Vishnevskiy in our group, uses regularization during least-squares refinements by a full set of calculated restraints and allows adjusting the weight of theoretical input into analysis of experimental data. For the first time we want to combine this approach with structural information gained by other methods like microwave spectroscopy. It will also be tried to apply specialized forms of crystallization (in-situ crystallization) to obtain suitable specimen for XRD experiments. In combination with gas-phase data of free molecules this will give information on the molecular structure distortions by changing the phase. These will also allow studying the charge density distribution of the functionalized carborane clusters, and consequently gaining insight into further molecular properties relevant for their use in SAM-based material chemistry.

这是一个捷克/德国联合合作项目的申请。捷克部分已由捷克共和国科学院无机化学研究所的Drahomir Hnyk博士提交给捷克科学基金会。该项目旨在确定官能化碳硼烷簇分子的结构，即官能化二碳-闭-癸硼烷（1，2-C2 B8 H10）和1，2-二碳-闭-十二硼烷（1，2-C2 B10 H12），其中一些末端氢原子被EH单元取代（其中E = S、Se、Te）。这些化合物将被布拉格小组用作建筑上刚性的建筑砌块，作为自组装单层（SAM）基材料的一部分。基础分子的结构数据的知识对于这些化合物在该领域的应用是重要的。由于化合物的结晶能力有限，通过结构化学的标准方法X射线衍射（XRD）来确定这种硼簇分子的分子结构通常是困难的。因此，我们想应用气体电子衍射（GED）来研究气态分子的无扰结构。比勒费尔德集团是全球为数不多的GED设备运营中心之一。除了纯结构测定，这些化合物是进一步开发GED数据分析新策略的理想候选者。这也将是该项目的一部分。这些发展旨在提高结构数据的精度、可靠性和再现性。Vishnevskiy博士在我们的小组中介绍的这种新的细化策略，在最小二乘细化过程中使用正则化，通过一套完整的计算约束，并允许调整理论输入到实验数据分析中的权重。这是我们第一次将联合收割机与其他方法如微波光谱学所获得的结构信息相结合。还将尝试应用特殊形式的结晶（原位结晶）来获得用于XRD实验的合适样品。与自由分子的气相数据相结合，这将给出通过改变相而引起的分子结构畸变的信息。这些还将允许研究官能化碳硼烷簇的电荷密度分布，并因此深入了解与其在SAM基材料化学中的使用相关的进一步分子性质。

项目成果

Influence of Antipodally Coupled Iodine and Carbon Atoms on the Cage Structure of 9,12-I2-closo-1,2-C2B10H10: An Electron Diffraction and Computational Study.

• DOI: 10.1021/acs.inorgchem.5b02102
• 发表时间: 2015-12
• 期刊: Inorganic chemistry
• 影响因子: 4.6
• 作者: Y. Vishnevskiy;D. Tikhonov;C. Reuter;N. Mitzel;D. Hnyk;J. Holub;D. Wann;P. D. Lane;R. J. Berger;Stuart A. Hayes