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

The recognition mechanism of the 1,3-di (1-phenyl-1H-tetrazole-5-thiol) -acetylphenylhydrazone tweezer receptor for the halogen anions

作　　者：刘艳芝[1] 袁焜[1] 吕玲玲[1] 董晓宁[1] 朱元成[1] 左国防[1] 刘新文[1] 

机构地区：[1]天水师范学院生命科学与化学学院,甘肃高校新型分子材料设计与功能省级重点实验室,天水741001

出　　处：《原子与分子物理学报》2011年第5期809-815,共7页Journal of Atomic and Molecular Physics

基　　金：天水师范学院"青蓝"人才工程基金;国家自然基金(51063006);教育部重点研究计划(211189)

摘　　要：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ΔE_(CP)分别为-327.5,-163.5和-148.3kJ·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^-.The recognition mechanism of the 1,3-di （1-phenyl-lH-tetrazole-5-thiol）-acetylphenylhydrazone 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- , C1- 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 kJmol-1 （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 investi- gate 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 the DAPHZ tweezer receptor for the halogen anions are in the order of DAPHZ...F-〉〉 DAPHZ...C1-≈ DAPHZ...Br .

关 键 词：分子识别 钳形受体 卤素阴离子 红移氢键 

分 类 号：O641[理学—物理化学]