乙腈溶剂中芳酰基硫脲对F^-识别作用的理论研究  

A DFT study on recognition between aroylthiourea and fluoride anion and spectral changes in acetonitrile

作　　者：别同玉[1] 

机构地区：[1]淮阴卫生高等职业技术学校,江苏淮安223300

出　　处：《化学研究与应用》2013年第5期675-683,共9页Chemical Research and Application

基　　金：淮安市科技支撑计划基金项目(HAG2012007)资助

摘　　要：采用混合密度泛函B3LYP方法,在6-31G**水平上和URHF溶剂半径中优化乙腈溶剂中四种芳酰基硫脲及其氟离子复合物的几何构型,从几何结构参数、电荷布居、前线轨道、结合能以及热力学参数等角度探讨复合物形成过程中主客体间的相互作用,结果表明,芳酰基硫脲在乙腈溶液中识别氟离子是一个自发过程,识别作用主要是硫脲氮氢与氟离子的氢键作用。受体分子识别氟离子能力与取代基密切相关,以N-对硝基苯基-N'-对硝基苯甲酰基硫脲氟离子复合物最稳定。在基态结构的基础上用相同的理论水平计算了乙腈溶剂中四种受体分子及氟离子复合物的电子吸收光谱。结果表明,有取代基的芳酰基硫脲识别氟离子后的光谱行为变化大,有利于使用比色法检测阴离子。光谱理论计算值很好地反映了实测值,这为实验室开展工作提供了依据。The structures of the aroyhhiourea derivatives and their fluoride anion complex in acetonitrile were optimized by density functional theory B3LYP method at the 6-31 ＋＋G＊ level and urhf solvation radii. The interaction between the aroyhhiourea deriva- tives and the fluoride anion were investigated by analyzing the geometric parameters, charge population, frontier orbital,binding en- ergy and thermodynamic parameters. The results show that the recognition interaction between fluoride anion and aroylthiourea is spontaneous and the capability is closely connected with the substituent. Among the aroylthiourea derivatives considered, the interac- tion of N-（4-nitro）phenyl-N＇-（4-nitro） benzoyl-sulfourea with F- is most easily. The absorption wavelengths were investigated based on the corresponding stable structures in acetonitrile. The results indicate that the introduced substituents are useful for the absorption bands red shifting of the complexes of the aroylthiourea derivatives with F-,which agrees well with the experimental results of anion recognition of aroylthiourea reported in the literature.

关 键 词：芳酰基硫脲 氟离子 识别 密度泛函理论 电子光谱 

分 类 号：O621.1[理学—有机化学]