杯[4]吡咯-卤素、铵离子复合物的理论研究  

Theoretical Study of Calix[4]pyrrole Complexes with Halide and Ammonium Ions

作　　者：陈雪松[1] 路鹏飞[1] 董玉慧[2] 解菊[1] 

机构地区：[1]扬州大学化学化工学院,江苏扬州225002 [2]潍坊科技学院,山东潍坊262700

出　　处：《物理化学学报》2013年第10期2187-2197,共11页Acta Physico-Chimica Sinica

基　　金：国家自然科学基金(21103147)资助项目~~

摘　　要：采用密度泛函理论的M06-2X/6-31G(d,p)方法对杯[4]吡咯(CP)与卤素离子(X=F,Cl,Br)及卤素-铵根离子对的各种可能组装体系进行了系统研究.详细讨论了各体系的结构、结合能、自然键轨道分析(NBO)和Multiwfn波函数分析的情况.结果显示杯[4]吡咯与卤素阴离子的相互作用主要是氢键,波函数分析显示在CPCl和CP-Br复合物中长程范德华力和空间位阻作用也明显存在.杯[4]吡咯能与卤素-铵根离子形成稳定的复合物,主要通过氢键作用、阴-阳离子的静电作用以及阳离子π相互作用.从理论上探讨了杯[4]吡咯与离子或离子对的2:1组装体系,但相对于1:1组装体系来讲,2:1体系并不占优势.本文结果进一步表明,杯[4]吡咯不仅是一种阴离子受体,而且也是一种良好的离子对受体,尤其是对涉及氟离子的客体,更是如此.Density functional theory M06-2X/6-31G（d, p） was used on complexes of calix[4]pyrrole （CP） with halide anions （X-=F-, Cl-, Br-） and NH;-X- ion-pairs. Geometries, binding energies, natural bond orbital analysis, and multifunctional wave function analysis （Multiwfn） were presented in detail. The results indicated that the interaction between the calix[4]pyrrole and halide anions mainly involved hydrogen （H）- bonds. Long-range van der Waals forces and steric effects were determined in the CP-Cl- and CP-Br- systems by Multiwfn analysis. Calix[4]pyrrole forms stable complexes with NH4＋-X- ion-pairs mainly through H-bonds and electrostatic interactions, as well as via cation-πinteractions. The 2：1 complexes of CP and anions or ion-pairs were also considered theoretically, but 2：1 is not the dominant stoichiometry relative to the 1：1 complexes. The current study also demonstrates that calix[4]pyrrole functions not only as an anion receptor, but also as a good ion-pair receptor, especially in cases involving fluoride ions.

关 键 词：杯[4]吡咯 阴离子及离子对 主客体相互作用 量子化学计算 

分 类 号：O641.1[理学—物理化学]