Key Laboratory of Colloid and Interface Chemistry, Shandong University, Ministry of Education, Jinan 250100, People's Republic of China.
J Mol Model. 2011 Nov;17(11):2817-23. doi: 10.1007/s00894-011-0974-y. Epub 2011 Feb 2.
The cooperativity between hydrogen and halogen bonds in XY···HNC···XY (X, Y = F, Cl, Br) complexes was studied at the MP2/aug-cc-pVTZ level. Two hydrogen-bonded dimers, five hydrogen-bonded dimers, and ten trimers were obtained. The hydrogen- and halogen-bonded interaction energies in the trimers were larger than those in the dimers, indicating that both the hydrogen bonding interaction and the halogen bonding interaction are enhanced. The binary halogen bonding interaction plays the most important role in the ternary system. The hydrogen donor molecule influences the magnitude of the halogen bonding interaction much more than the hydrogen bonding interaction in the trimers with respect to the dimers. Our calculations are consistent with the conclusion that the stronger noncovalent interaction has a bigger effect on the weaker one. The variation in the vibrational frequency in the HNC molecule was considered. The NH antisymmetry vibration frequency has a blue shift, whereas the symmetry vibration frequency has a red shift. A dipole moment enhancement is observed upon formation of the trimers. The variation in topological properties at bond critical points was obtained using the atoms in molecules method, and was consistent with the results of the interaction energy analysis.
在 MP2/aug-cc-pVTZ 水平上研究了 XY···HNC···XY（X，Y = F，Cl，Br）复合物中氢键和卤键之间的协同作用。得到了两个氢键二聚体、五个氢键三聚体和十个三聚物。三聚体中的氢键和卤键相互作用能大于二聚体中的相互作用能，表明氢键相互作用和卤键相互作用都得到了增强。二元卤键相互作用在三元体系中起着最重要的作用。对于三聚体，与二聚体相比，氢给体分子对卤键相互作用的影响比对氢键相互作用的影响大得多。我们的计算结果与以下结论一致，即较强的非共价相互作用对较弱的相互作用影响更大。考虑了 HNC 分子中振动频率的变化。NH 反对称振动频率蓝移，而对称振动频率红移。形成三聚体时观察到偶极矩增强。使用分子中的原子方法获得了键临界点处拓扑性质的变化，与相互作用能分析的结果一致。
