College of Chemistry and Material Science, Hebei Normal University, Road East of 2nd Ring South, Shijiazhuang, 050024, China.
Key Laboratory of Inorganic Nano-materials of Hebei Province, Shijiazhuang, 050024, China.
J Mol Model. 2019 Jan 4;25(1):19. doi: 10.1007/s00894-018-3895-1.
As a kind of intermolecular noncovalent interaction, chalcogen bonding plays a critical role in the fields of chemistry and biology. In this paper, S⋅⋅⋅S chalcogen bonds in three groups of complexes, FP(S)N⋅⋅⋅SX, FPNS⋅⋅⋅SX, and FPSN⋅⋅⋅SX (X = F, Cl, Br, OH, CH, NH), were investigated at the MP2/aug-cc-pVTZ level of theory. The calculated results show that the formation of S⋅⋅⋅S chalcogen bond is in the manner of attraction between the positive molecular electrostatic potential (V) of chalcogen bond donator and the negative V of chalcogen bond acceptor. It is found that a good correlation exists between the S⋅⋅⋅S bond length and the interaction energy. The energy decomposition indicates the electrostatic energy and polarization energy are closely correlated with the total interaction energy. NBO analysis reveals that the charge transfer is rather closely correlated with the polarization, and the charge transfer has a similar behavior as the polarization in the formation of complex. Our results provide a new example for interpreting the noncovalent interaction based on the σ-hole concept. Graphical abstract The chalcogen bonds in the studied binary complexes are Coulombic in nature, and the charge transfer has a similar behavior as the polarization in the formation of the complex.
作为一种分子间非共价相互作用，硫属键在化学和生物学领域中起着关键作用。在本文中，我们在 MP2/aug-cc-pVTZ 理论水平上研究了三组配合物 FP(S)N⋅⋅⋅SX、FPNS⋅⋅⋅SX 和 FPSN⋅⋅⋅SX（X = F、Cl、Br、OH、CH、NH）中的 S⋅⋅⋅S 硫属键。计算结果表明，S⋅⋅⋅S 硫属键的形成方式是硫属键供体的正分子静电势（V）与硫属键受体的负 V 之间的吸引力。我们发现 S⋅⋅⋅S 键长与相互作用能之间存在很好的相关性。能量分解表明静电能和极化能与总相互作用能密切相关。NBO 分析表明电荷转移与极化密切相关，并且电荷转移在配合物的形成中具有与极化相似的行为。我们的结果为基于 σ-hole 概念解释非共价相互作用提供了一个新的例子。
