Laboratory of Characterizations, Applications and Modeling of Materials (LR18ES08), Department of Chemistry, University of Tunis El Manar, Tunis 1068, Tunisia.
Department de Química Inorgànica i Orgànica & IQTCUB, Universitat de Barcelona, Martí i Franquès 1-11, 08028 Barcelona, Spain.
Int J Mol Sci. 2024 Jul 8;25(13):7497. doi: 10.3390/ijms25137497.
The noncovalent chalcogen interaction between SO/SO and diazines was studied through a dispersion-corrected DFT Kohn-Sham molecular orbital together with quantitative energy decomposition analyses. For this, supramolecular circular chains of up to 12 molecules were built with the aim of checking the capability of diazine molecules to detect SO/SO compounds within the atmosphere. Trends in the interaction energies with the increasing number of molecules are mainly determined by the Pauli steric repulsion involved in these σ-hole/π-hole interactions. But more importantly, despite the assumed electrostatic nature of the involved interactions, the covalent component also plays a determinant role in its strength in the involved chalcogen bonds. Noticeably, π-hole interactions are supported by the charge transfer from diazines to SO/SO molecules. Interaction energies in these supramolecular complexes are not only determined by the S···N bond lengths but attractive electrostatic and orbital interactions also determine the trends. These results should allow us to establish the fundamental characteristics of chalcogen bonding based on its strength and nature, which is of relevance for the capture of sulfur oxides.
通过色散校正的 DFT Kohn-Sham 分子轨道和定量能量分解分析，研究了 SO/SO 和二嗪之间的非共价硫属元素相互作用。为此，构建了多达 12 个分子的超分子环状链，目的是检查二嗪分子在大气中检测 SO/SO 化合物的能力。随着分子数量的增加，相互作用能的趋势主要取决于这些 σ-hole/π-hole 相互作用中涉及的 Pauli 位阻。但更重要的是，尽管所涉及的相互作用被认为具有静电性质，但共价成分在涉及的硫属键的强度中也起着决定性的作用。值得注意的是，π-hole 相互作用得到了二嗪向 SO/SO 分子的电荷转移的支持。这些超分子配合物中的相互作用能不仅取决于 S···N 键长，而且吸引力静电和轨道相互作用也决定了趋势。这些结果应该使我们能够根据其强度和性质建立硫属键的基本特征，这对于捕获硫氧化物具有重要意义。
