College of Chemistry and Chemical Engineering, and Henan Key Laboratory of Function-Oriented Porous Materials, Luoyang Normal University, Luoyang 471934, China.
Molecules. 2022 Feb 13;27(4):1252. doi: 10.3390/molecules27041252.
The bifurcated σ-hole···σ-hole stacking interactions between organosulfur molecules, which are key components of organic optical and electronic materials, were investigated by using a combined method of the Cambridge Structural Database search and quantum chemical calculation. Due to the geometric constraints, the binding energy of one bifurcated σ-hole···σ-hole stacking interaction is in general smaller than the sum of the binding energies of two free monofurcated σ-hole···σ-hole stacking interactions. The bifurcated σ-hole···σ-hole stacking interactions are still of the dispersion-dominated noncovalent interactions. However, in contrast to the linear monofurcated σ-hole···σ-hole stacking interaction, the contribution of the electrostatic energy to the total attractive interaction energy increases significantly and the dispersion component of the total attractive interaction energy decreases significantly for the bifurcated σ-hole···σ-hole stacking interaction. Another important finding of this study is that the low-cost spin-component scaled zeroth-order symmetry-adapted perturbation theory performs perfectly in the study of the bifurcated σ-hole···σ-hole stacking interactions. This work will provide valuable information for the design and synthesis of novel organic optical and electronic materials.
采用剑桥结构数据库搜索和量子化学计算相结合的方法，研究了有机硫分子之间的分叉 σ-孔···σ-孔堆积相互作用，这些有机硫分子是有机光学和电子材料的关键组成部分。由于几何限制，一个分叉 σ-孔···σ-孔堆积相互作用的结合能通常小于两个自由单分叉 σ-孔···σ-孔堆积相互作用的结合能之和。分叉 σ-孔···σ-孔堆积相互作用仍然是色散主导的非共价相互作用。然而，与线性单分叉 σ-孔···σ-孔堆积相互作用相比，静电能对总吸引相互作用能的贡献显著增加，而分叉 σ-孔···σ-孔堆积相互作用的总吸引相互作用能的色散分量显著减少。这项研究的另一个重要发现是，低成本的自旋分量标度零阶对称自适应微扰理论在分叉 σ-孔···σ-孔堆积相互作用的研究中表现完美。这项工作将为新型有机光学和电子材料的设计和合成提供有价值的信息。
