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

在本项目中，我们研究了Sb、Bi和Te原子化合物中色散相互作用的作用，结合量子化学计算和x射线晶体学表征合成了相应的化合物。在该项目的第一个资助期，发现这些原子之间以弥散为主的非共价相互作用以及与芳烃的pi系统对其化合物的晶体结构的形成起决定性作用。它们还显著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吸电子配体的影响成为焦点。它们的作用一方面需要借助量子化学计算来预测，其中分子间微扰理论及其定量计算色散和进一步相互作用的可能性将发挥重要作用。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物质。此外，我们将合成具有刚性芳香配体的homo和hetero双金属配合物，这允许调整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。通过对含有15和16族金属原子的化合物与测试粒子相互作用的分子间摄动理论计算，利用结果对分子和分子聚集体的结构进行定性预测，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.