论文部分内容阅读
采用密度泛函B3LYP(Bccke.thrcc-paramctcr,Lee-Yang-Parr)方法探讨了间-苯二氧乙酰-(N-苯甲酰基)肼(DAPHZ)受体对卤素阴离子的识别机理,结果发现DAPHZ钳形受体C构型以其钳形结构中的N-H键与卤素阴离子间形成多齿红移氢键进行识别,其中C…X~-(X=F~-,Cl~-和Br~-)体系中主客体间以双齿氢键识别结合,而在C…I~-体系中主客体间以三齿氢键识别结合,说明钳形受体C对I~-在空间几何上具有最好的匹配性.经BSSE校正后的C…F~-,C…Cl~-,C…Br~-和C…I~-体系分子识别相互作用能△E_(CP)分别为-314.0,-200.1,-183.3和-136.3 kJmol~(-1),说明钳形受体C对F~-在热力学上具有最好的识别能力.此外,采用自然键轨道(NBO))分析及分子中原子(AIM)等理论分析了C…X~-(X=F~-,Cl~-,Br~-和I~-)识别体系中红移氢键的电子结构和性质.
The recognition mechanism of the halogen anions by m-phenylenedioxyacetyl- (N-benzoyl) hydrazine (DAPHZ) receptor was investigated by density functional theory B3LYP (Bccke.thrcc-paramctcr, Lee-Yang-Parr) The C configuration of the DAPHZ pincer receptor is identified by the formation of multidentate redshift hydrogen bonds between NH bonds and halogen anions in the pincer structure, where C ... X ~ - (X = F ~ -, Cl ~ - and Br ~ -) system to identify the binding between the host and guest by bidentate hydrogen bonds, while in C ... I ~ - system identified by the three-tooth hydrogen bond between the host and guest, Clamp receptor C on I ~ - in the spatial geometry with The best matching is that the molecular recognition interaction energy △ E_ (CP) of C ... F ~ -, C ... Cl ~ -, C ... Br ~ - and C ... I ~ -200.1, -183.3 and -136.3 kJ mol ~ (-1), indicating that the clavicle receptor C has the best thermodynamic discrimination ability for F ~ .In addition, using the analysis of the natural bond orbital (NBO) (AIM) and other theories were used to analyze the electronic structures and properties of redox hydrogen bonds in C ... X ~ - (X = F ~ -, Cl ~ -, Br ~ - and I ~ -) recognition systems.