Citation: CHEN Xue-Song, LU Peng-Fei, DONG Yu-Hui, XIE Ju. Theoretical Study of Calix[4]pyrrole Complexes with Halide and AmmoniumIons[J]. Acta Physico-Chimica Sinica, 2013, 29(10): 2187-2197. doi: 10.3866/PKU.WHXB201308142
杯[4]吡咯-卤素、铵离子复合物的理论研究
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.
English
Theoretical Study of Calix[4]pyrrole Complexes with Halide and AmmoniumIons
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 od ion-pair receptor, especially in cases involving fluoride ions.
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-
[1]
(1) Gale, P. A.; Anzenbacher, P.; Sessler, J. L. Coord. Chem. Rev.2001, 222, 57. doi: 10.1016/S0010-8545(01)00346-0
(1) Gale, P. A.; Anzenbacher, P.; Sessler, J. L. Coord. Chem. Rev.2001, 222, 57. doi: 10.1016/S0010-8545(01)00346-0
-
[2]
(2) Allen, W. E.; Gale, P. A.; Brown, C. T.; Lynch, V. M.; Sessler, J.L. J. Am. Chem. Soc. 1996, 118, 12471. doi: 10.1021/ja9632217(2) Allen, W. E.; Gale, P. A.; Brown, C. T.; Lynch, V. M.; Sessler, J.L. J. Am. Chem. Soc. 1996, 118, 12471. doi: 10.1021/ja9632217
-
[3]
(3) Rambo, B. M.; Sessler, J. L. Chem. Eur. J. 2011, 17, 4946. doi: 10.1002/chem.v17.18(3) Rambo, B. M.; Sessler, J. L. Chem. Eur. J. 2011, 17, 4946. doi: 10.1002/chem.v17.18
-
[4]
(4) Cafeo, G.; Carbotti, G.; Cuzzola, A.; Fabbi, M.; Ferrini, S.;Kohnke, F. H.; Papanikolaou, G.; Plutino, M. R.; Rosano, C.;White, A. J. P. J. Am. Chem. Soc. 2013, 135, 2514 .(4) Cafeo, G.; Carbotti, G.; Cuzzola, A.; Fabbi, M.; Ferrini, S.;Kohnke, F. H.; Papanikolaou, G.; Plutino, M. R.; Rosano, C.;White, A. J. P. J. Am. Chem. Soc. 2013, 135, 2514 .
-
[5]
(5) Blas, J. R.; Marquez, M.; Sessler, J. L.; Luque, F. J.; Orozco, M.J. Am. Chem. Soc. 2002, 124, 12796. doi: 10.1021/ja020318m(5) Blas, J. R.; Marquez, M.; Sessler, J. L.; Luque, F. J.; Orozco, M.J. Am. Chem. Soc. 2002, 124, 12796. doi: 10.1021/ja020318m
-
[6]
(6) Wu, Y. D.; Wang, D. F.; Sessler, J. L. J. Org. Chem. 2001, 66,3739. doi: 10.1021/jo0016273(6) Wu, Y. D.; Wang, D. F.; Sessler, J. L. J. Org. Chem. 2001, 66,3739. doi: 10.1021/jo0016273
-
[7]
(7) Pichierri, F. J. Mol. Struct. 2002, 581, 117.(7) Pichierri, F. J. Mol. Struct. 2002, 581, 117.
-
[8]
(8) Wintergerst, M. P.; Levitskaia, T. G.; Moyer, B. A.; Sessler, J.L.; Delmau, L. H. J. Am. Chem. Soc. 2008, 130, 4129.(8) Wintergerst, M. P.; Levitskaia, T. G.; Moyer, B. A.; Sessler, J.L.; Delmau, L. H. J. Am. Chem. Soc. 2008, 130, 4129.
-
[9]
(9) Kriz, J.; Dybal, J.; Makrlik, E.; Sedlakova, Z. J. Chem. Phys.2012, 400, 19.(9) Kriz, J.; Dybal, J.; Makrlik, E.; Sedlakova, Z. J. Chem. Phys.2012, 400, 19.
-
[10]
(10) Xia, Y.; Wang, X.; Zhang, Y.; Luo, B.; Liu, Y. Journal of Molecular Modeling 2012, 18 (6), 2291.(10) Xia, Y.; Wang, X.; Zhang, Y.; Luo, B.; Liu, Y. Journal of Molecular Modeling 2012, 18 (6), 2291.
-
[11]
(11) Blas, J. R.; Marquez, M.; Sessler, J. L.; Luque, F. J.; Orozco, M.Chem. Eur. J. 2007, 13, 1108.(11) Blas, J. R.; Marquez, M.; Sessler, J. L.; Luque, F. J.; Orozco, M.Chem. Eur. J. 2007, 13, 1108.
-
[12]
(12) Zhao, Y.; Truhlar, D. G. Accounts Chem. Res. 2008, 41, 157.doi: 10.1021/ar700111a(12) Zhao, Y.; Truhlar, D. G. Accounts Chem. Res. 2008, 41, 157.doi: 10.1021/ar700111a
-
[13]
(13) Zhao, Y.; Truhlar, D. G. Theor. Chem. Acc. 2008, 120, 215. doi: 10.1007/s00214-007-0310-x(13) Zhao, Y.; Truhlar, D. G. Theor. Chem. Acc. 2008, 120, 215. doi: 10.1007/s00214-007-0310-x
-
[14]
(14) Sun, T.; Wang, Y. B. Acta Phys. -Chim. Sin. 2011, 27 (11), 2553.[孙涛, 王一波.物理化学学报, 2011, 27 (11), 2553.] doi: 10.3866/PKU.WHXB20111017(14) Sun, T.; Wang, Y. B. Acta Phys. -Chim. Sin. 2011, 27 (11), 2553.[孙涛, 王一波.物理化学学报, 2011, 27 (11), 2553.] doi: 10.3866/PKU.WHXB20111017
-
[15]
(15) Weinhold, F.; Schleyer, P. v. R.; Clark, T.; Gasteiger, J.;Kollman, P. A.; SchaeferI, H. F., III; Schreiner, P. R.Encyclopedia of Computational Chemistry; John Wiley& Sons:Chichester, UK, 1998; Vol. 3, pp 1792-1811.(15) Weinhold, F.; Schleyer, P. v. R.; Clark, T.; Gasteiger, J.;Kollman, P. A.; SchaeferI, H. F., III; Schreiner, P. R.Encyclopedia of Computational Chemistry; John Wiley& Sons:Chichester, UK, 1998; Vol. 3, pp 1792-1811.
-
[16]
(16) Frish, M. J.; Trucks, G. W.; Schlegel, H. B.; et al . Gaussian 09,Revision B1; Gaussian Inc.: Wallingford, CT, 2010.(16) Frish, M. J.; Trucks, G. W.; Schlegel, H. B.; et al . Gaussian 09,Revision B1; Gaussian Inc.: Wallingford, CT, 2010.
-
[17]
(17) Johnson, E. R.; Keinan, S.; Mori-Sanchez, P.; Contreras-Garcia,J.; Cohen, A. J.; Yang, W. J. Am. Chem. Soc. 2010, 132, 6498.(17) Johnson, E. R.; Keinan, S.; Mori-Sanchez, P.; Contreras-Garcia,J.; Cohen, A. J.; Yang, W. J. Am. Chem. Soc. 2010, 132, 6498.
-
[18]
(18) Lu, T.; Chen, F. J. Comput. Chem. 2012, 33, 580.(18) Lu, T.; Chen, F. J. Comput. Chem. 2012, 33, 580.
-
[19]
(19) Chen, P. Q.; Sun, H. W.; Chen, L.; Shen, R. X.; Yuan, M. X.;Lai, C. M. Chem. J. Chin. Univ. 2004, 25 (12), 2290. [陈沛全,孙宏伟,陈兰,沈荣欣, 袁满雪,赖城明.高等学校化学学报,2004, 25 (12), 2290.](19) Chen, P. Q.; Sun, H. W.; Chen, L.; Shen, R. X.; Yuan, M. X.;Lai, C. M. Chem. J. Chin. Univ. 2004, 25 (12), 2290. [陈沛全,孙宏伟,陈兰,沈荣欣, 袁满雪,赖城明.高等学校化学学报,2004, 25 (12), 2290.]
-
[20]
(20) Liu, K.; Guo, Y.; Xu, J.; Shao, S. J.; Jiang, S. X. Chinese Chemical Letters 2006, 17 (3), 387.
(20) Liu, K.; Guo, Y.; Xu, J.; Shao, S. J.; Jiang, S. X. Chinese Chemical Letters 2006, 17 (3), 387.
-
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