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Cation sitting in aromatic cages: ab initio computational studies on tetramethylammonium–(benzene) n ( n =3–4) complexes
Author(s) -
Cheng Jiagao,
Gong Zhen,
Zhu Weiliang,
Tang Yun,
Li Weihua,
Li Zhong,
Jiang Hualiang
Publication year - 2007
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.1175
Subject(s) - benzene , tetramethylammonium , chemistry , ab initio , aromaticity , crystallography , computational chemistry , molecule , ring (chemistry) , ab initio quantum chemistry methods , ion , organic chemistry
Quantum chemistry study was performed on interaction between tetramethylammonium (TMA) and aromatic cages by means of the MP2 method to show how TMA sits in an aromatic cage that is composed of benzenes. The MP2 calculations on TMA–(benzene) n complexes demonstrate that the more the benzene molecules in the aromatic cage, the stronger the binding strength between the cage and TMA. In details, the structure of TMA–(benzene) n ( n = 1–4) complexes can be easily constructed by superimposing n TMA‐benzene complexes via TMA, and the binding energies of the TMA–(benzene) n complexes are the sum of the n corresponding TMA‐benzene systems. For instance, the distances between the N of TMA and the plane of the benzene ring are 4.238, 4.252, 4.264 ,and 4.276 Å, respectively, for TMA–(benzene) n ( n = 1–4) complexes, and the BSSE corrected binding energies at MP2/6‐311++G** level are −8.8, −17.3, −25.8 and −34.3 kcal/mol, respectively, for TMA– (benzene) n ( n = 1–4) complexes. Thus, this study provides us useful information on how a cation interacts with an aromatic cage in terms of complex geometry and binding strength. Copyright © 2007 John Wiley & Sons, Ltd.