1,3-双(1-苯基-1H-四唑-5-巯基)-乙酰苯腙钳形受体对卤素阴离子的识别机理

摘要

The recognition mechanism of the 1, 3-di(l-phenyl-lH-tetrazole-5-thiol)-acetylphenylhydra-zone tweezers receptor (DAPHZ) for the halogen anions was discussed at the density function Becke, three-parameter, Lee-Yang-Parr (B3LYP) and Hatree-Fock (HF) methods. The results showed that recognition mechanism was performed by using red-shift hydrogen bond between N - H bonds of the DAPHZ and the halogen anions X~ (X = F~ , Cl~ and Br~ ). The calculated interaction energies (Aecp) with basis set super-position error (BSSE) correction of the three complexes are -327. 5 , - 163. 5 and - 148. 3 kjmor1 (HF/3-21G), respectively. Natural bond orbital theory (NBO) analysis, Atoms in molecules (AIM) theory and the chemical shift calculation of the related atoms has been used to investigate the electronic structure and properties of the red-shift hydrogen bond between N-H bonds of the DAPHZ and the halogen anions X" , and the results revealed that the relative recognition ability of theDAPHZ tweezer receptor for the halogen anions are in the order of DAPHZ-F" DAPHZ"*C1~?5DAPHZ-Br'.%要采用密度泛函B3LYP(Becke,three-parameter,Lee-Yang-parr)和HF(Hatree-Fock)方法,从理论上探讨了1,3-双(1-苯基-1H-四唑-5-巯基)-乙酰苯腙(DAPHZ)钳形受体对卤素阴离子的识别机理,结果发现DAPHZ受体以其钳形结构中的-N-H基团与卤素阴离子间形成双侧红移氢键进行识别.经BSSE校正后DAPHZ…F-,DAPHZ…Cl-和DAPHZ…Br-体系的分子识别相互作用能△EcP分别为-327.5,-163.5和-148.3 kJ·mol-1,说明钳形DAPHZ受体对F-具有最好的识别能力.此外,采用自然键轨道(NBO)计算,相关H原子化学位移计算及分子中原子(AIM)等理论分析了识别体系中红移氢键的电子结构和性质,结果表明APHZ受体对卤素阴离子的识别能力的相对顺序为DAPHZ…F-＞＞DAPHZ…Cl-≈DAPHZ…Br-.