Combined Quantum Chemical and Experimental Study on Metal-Metal Interactions in Heavy Group15 and Group16 Compounds

在这个项目中，我们研究了弥散相互作用在Sb，Bi和Te原子化合物中的作用，结合了相应化合物的合成和量子化学计算，并通过X射线结晶学对其结构进行了表征。在该项目的第一个资助期，发现这些原子之间以及与芳烃的pi体系之间以分散为主的非共价相互作用对其化合物的晶体结构的形成具有决定性作用。它们还有助于稳定含有几个非共价连接的重基团15/16金属原子的分子的构象，并可能导致例如键角低于90度。在第二个资助期，金属原子的供电子和引出配体的影响成为关注的焦点。一方面，它们的影响将借助量子化学计算来预测，其中分子间微扰理论及其可能的色散和进一步相互作用的定量计算将发挥重要作用。另一方面，我们将合成和结构表征具有特别强相互作用的有前途的候选者。此外，我们还将合成具有刚性芳香族配体的同、异双金属配合物，这允许调节金属原子之间的距离。它对分子内和分子间相互作用的影响应通过结构表征和量子化学计算来理解。通过分子间微扰理论计算含第15族和第16族金属原子的化合物与测试粒子的相互作用，利用这些结果定性地预测分子和分子聚集体的结构，可以更好地理解吸引色散和排斥力组合的各向异性。

In this project we investigate the role of dispersion interactions in chemical compounds of the atoms Sb, Bi, and Te, combining synthesis of corresponding compounds with quantum chemical calculations and structural characterization via X-ray crystallography. In the first funding period of the project dispersion-dominated non-covalent interactions between these atoms and with pi systems of arenes were found to be decisive for the formation of crystal structures of their compounds. They also significantly contribute to the stabilization of conformers of molecules containing several non-covalently linked heavy group 15/16 metal atoms and may cause, for example bond angles below 90 degree. In the second funding period the influence of electron-donating and -withdrawing ligands of the metal atoms comes into focus. Their effects on the one hand shall be predicted with the help of quantum chemical calculations, where intermolecular perturbation theory with its possibility of quantitative computation of dispersion and further interactions will play an important role. On the other hand we will synthesize and structurally characterize promising candidates with particularly strong interactions. Furthermore we will synthesize homo and hetero bimetallic complexes with rigid aromatic ligands, which allow for a tuning of the distance between the metal atoms. Its consequences on intra- and intermolecular interactions shall be understood through structural characterization and quantum chemical calculation. An improved understanding of the anisotropy of the combination of attractive dispersion and repulsive steric forces shall be achieved through intermolecular perturbation theory calculations of the interactions of chemical compounds containing group 15 and 16 metal atoms with test particles, utilizing the results for qualitative predictions of the structures of molecules and molecular aggregates.