Comparative study of halogen- and hydrogen-bond interactions between benzene derivatives and dimethyl sulfoxide.
Comparative study of halogen- and hydrogen-bond interactions between benzene derivatives and dimethyl sulfoxide.
复制标题
DOI：
10.1002/cphc.201500324
复制
发表时间：
2015-08
期刊：
影响因子：
--
通讯作者：
Yan‐Zhen Zheng;Geng Deng;Yu Zhou;Hai-Yuan Sun;Zhi‐Wu Yu
中科院分区：
文献类型：
--
作者：
Yan‐Zhen Zheng;Geng Deng;Yu Zhou;Hai-Yuan Sun;Zhi‐Wu Yu
卤键与氢键一样，是一种重要的非共价相互作用，在许多化学领域中起着重要的作用。本文利用红外光谱、核磁共振谱和从头算研究了两种苯衍生物（C6 F5 Br和C6 F5 I）与二甲基亚砜（DMSO）之间的溴和碘卤素键相互作用.并与C6 F5 Cl/C6 F5 H与DMSO相互作用的结果进行了比较。首先，氢键的相互作用能比溴基和氯基卤键的相互作用能强，但比碘基卤键弱。第二，吸引能依赖于1/r（n），其中对于氢键和卤键，n都在3和4之间，而所有的排斥能都依赖于1/r（8.5）。第三，卤键的方向性大于氢键。溴基和碘基卤键在这方面是严格的，氯基卤键仅略微偏离180°。方向顺序为碘基卤键>溴基卤键>氯基卤键>氢键。第四，在形成氢键和卤素键时，电荷从DMSO转移到氢键和卤素键供体。CH 3基团对络合物的稳定性有积极的贡献。
The halogen bond, similar to the hydrogen bond, is an important noncovalent interaction and plays important roles in diverse chemistry-related fields. Herein, bromine- and iodine-based halogen-bonding interactions between two benzene derivatives (C6 F5 Br and C6 F5 I) and dimethyl sulfoxide (DMSO) are investigated by using IR and NMR spectroscopy and ab initio calculations. The results are compared with those of interactions between C6 F5 Cl/C6 F5 H and DMSO. First, the interaction energy of the hydrogen bond is stronger than those of bromine- and chlorine-based halogen bonds, but weaker than iodine-based halogen bond. Second, attractive energies depend on 1/r(n) , in which n is between three and four for both hydrogen and halogen bonds, whereas all repulsive energies are found to depend on 1/r(8.5) . Third, the directionality of halogen bonds is greater than that of the hydrogen bond. The bromine- and iodine-based halogen bonds are strict in this regard and the chlorine-based halogen bond only slightly deviates from 180°. The directional order is iodine-based halogen bond>bromine-based halogen bond>chlorine-based halogen bond>hydrogen bond. Fourth, upon the formation of hydrogen and halogen bonds, charge transfers from DMSO to the hydrogen- and halogen-bond donors. The CH3 group contributes positively to stabilization of the complexes.