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Effects of solvent on weak halogen bonds: Density functional theory calculations
Author(s) -
Lu Yunxiang,
Li Haiying,
Zhu Xiang,
Liu Honglai,
Zhu Weiliang
Publication year - 2011
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.23125
Subject(s) - halogen bond , chemistry , halogen , intermolecular force , cyclohexane , hydrogen bond , solvation , solvent , density functional theory , computational chemistry , solvent effects , alkyl , molecule , organic chemistry
Abstract In recent years, many applications of solution‐phase halogen bonding in anion recognition, catalysis, and pseudorotaxane formation have been reported. Moreover, a number of thermodynamic data of halogen bonding interactions in organic solution are now available. To obtain detailed information of the influence of the surrounding medium on weak halogen bonds, a series of dimeric complexes of halobenzene (PhX) with three electron donors (H 2 O, HCHO, and NH 3 ) were investigated by means of DFT/PBE calculations in this work. The PCM implicit solvation approach was utilized to include the effects of three solvents (cyclohexane, chloroform, and water) as representatives for a wide range of dielectric constant. In some cases, halogen‐bond distances are shown to shorten in solution, accompanied by concomitant elongation of the CX bonds. For the remaining systems, the intermolecular distances tend to increase or remain almost unchanged under solvent effects. In general, the solvent has a slight destabilizing effect on weak halogen bonds; the strength order of halogen bonds observed in vacuum remains unchanged in liquid phases. Particularly, the interaction strength attenuates in the order I > Br > Cl in solution, consistent with the experimental measurements of weak halogen bond door abilities. The similarities between halogen and hydrogen bonding in solution were also elucidated. The results presented herein would be very useful in future applications of halogen bonding in molecular recognition and medicinal chemistry. © 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2012