物理化学学报 >> 2013, Vol. 29 >> Issue (10): 2187-2197.doi: 10.3866/PKU.WHXB201308142

理论与计算化学 上一篇    下一篇

杯[4]吡咯-卤素、铵离子复合物的理论研究

陈雪松1, 路鹏飞1, 董玉慧2, 解菊1   

  1. 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
  • 收稿日期:2013-05-21 修回日期:2013-08-08 发布日期:2013-09-26
  • 通讯作者: 解菊 E-mail:xieju@yzu.edu.cn
  • 基金资助:

    国家自然科学基金(21103147)资助项目

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

CHEN Xue-Song1, LU Peng-Fei1, DONG Yu-Hui2, XIE Ju1   

  1. 1 School of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou 225002, Jiangsu Province, P. R. China;
    2 Weifang University of Science and Technology, Weifang 262700, Shandong Province, P. R. China
  • Received:2013-05-21 Revised:2013-08-08 Published:2013-09-26
  • Contact: XIE Ju E-mail:xieju@yzu.edu.cn
  • Supported by:

    The project was supported by the National Natural Science Foundation of China (21103147).

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.

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

Abstract:

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 NH4+-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-π interactions. 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.

Key words: Calix[4]pyrrole, Anion and ion-pair, Host-guest interaction, Quantumchemistry calculation

MSC2000: 

  • O641