Halogen-bond and hydrogen-bond interactions between three benzene derivatives and dimethyl sulphoxide.
Halogen-bond and hydrogen-bond interactions between three benzene derivatives and dimethyl sulphoxide.
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DOI：
10.1039/c3cp55451a
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发表时间：
2014-03
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影响因子：
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通讯作者：
Yan‐Zhen Zheng;Nannan Wang;Yu Zhou;Zhi‐Wu Yu
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文献类型：
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作者：
Yan‐Zhen Zheng;Nannan Wang;Yu Zhou;Zhi‐Wu Yu
卤键和氢键一样，是一种非共价键相互作用，在化学、生物学和晶体工程等诸多领域都发挥着重要作用。本文对三种氟苯衍生物与二甲基亚砜（DMSO）之间的卤素/氢键相互作用进行了比较研究。利用衰减全反射红外光谱（ATR-IR）、核磁共振（NMR）和从头算方法，得到了一些结论。在MP2理论水平上，采用aug-cc-pVDZ基组，对单体和配合物的静电表面势、几何构型、能量、振动频率、强度和自然布居分析（NPA）进行了研究。结果表明：C_6F_5H-DMSO-C_6F_4H-DMSO> C_6F_5Cl-DMSO-C_6F_5H-DMSO-C_6F_4H-DMSO-C_6F_5Cl-DMSO-C_6F_5H-DMSO-C_6F_4H-DMSO-C_6F_5Cl-DMSO-C_6F_5Cl-DMSO-C_6F_5H-DMSO-C_6F_4H-DMSO-C_6F_5Cl-DMSO-C_6F_5Cl-DMSO-C_6F_6F_4H-DMSO-C_6F_5Cl-DMSO-C_6F_6F_5Cl-DMSO-C_6F_6F_4H-DMSO-C_6F_5Cl-DMSO-C_6F_6F_5Cl-DMSO-C_6F_6F_4H-DMSO-C_6F_5Cl-DMSO-C_6F_6F_5Cl-DMSO第二，分别建立了氢键和卤素键的吸引能对1/r（3.3）和1/r（3.1）的依赖关系。第三，在形成氢键和卤素键时，存在从DMSO到氢键和卤素键供体的电荷转移。发现背基CH 3对络合物的稳定性有积极的贡献。第四，在C_6F_5Cl-DMSO-d_6体系的ν（C-Cl）吸收带中检测到一个等吸光点，表明二元混合物中C_6F_5Cl只存在两种主要形式：非络合形式和卤键络合形式。在C6F5H-DMSO和ClC6F4H-DMSO体系中稳定复合物的存在通过具有固定位置的新峰的出现来证明。
Halogen-bonds, like hydrogen-bonds, are a kind of noncovalent interaction and play an important role in diverse fields including chemistry, biology and crystal engineering. In this work, a comparative study was carried out to examine the halogen/hydrogen-bonding interactions between three fluoro-benzene derivatives and dimethyl sulphoxide (DMSO). A number of conclusions were obtained by using attenuated total reflection infrared spectroscopy (ATR-IR), nuclear magnetic resonance (NMR) and ab initio calculations. Electrostatic surface potential, geometry, energy, vibrational frequency, intensity and the natural population analysis (NPA) of the monomers and complexes are studied at the MP2 level of theory with the aug-cc-pVDZ basis set. First, the interaction strength decreases in the order C6F5H-DMSO ∼ ClC6F4H-DMSO > C6F5Cl-DMSO, implying that the hydrogen-bond is stronger than the halogen-bond in the systems and, when interacting with ClC6F4H, DMSO favors the formation of a hydrogen-bond rather than a halogen-bond. Second, attractive energy dependences on 1/r(3.3) and 1/r(3.1) were established for the hydrogen-bond and halogen-bond, respectively. Third, upon the formation of a hydrogen-bond and halogen-bond, there is charge transfer from DMSO to the hydrogen-bond and halogen-bond donor. The back-group CH3 was found to contribute positively to the stabilization of the complexes. Fourth, an isosbestic point was detected in the ν(C-Cl) absorption band in the C6F5Cl-DMSO-d6 system, indicating that there exist only two dominating forms of C6F5Cl in binary mixtures; the non-complexed and halogen-bond-complexed forms. The presence of stable complexes in C6F5H-DMSO and ClC6F4H-DMSO systems are evidenced by the appearance of new peaks with fixed positions.