Tuning the C-X⋯π interaction of benzene-chloroacetylene complexes by aromatic substitutions

S. Karthikeyan; Jin Yong Lee

doi:10.1016/j.cplett.2014.04.010

Tuning the C-X⋯π interaction of benzene-chloroacetylene complexes by aromatic substitutions

S. Karthikeyan
, Jin Yong Lee

Department of Chemistry

Sungkyunkwan University

Research output: Contribution to journal › Article › peer-review

7 Scopus citations

Abstract

The interaction between chloroacetylene (C₂HCl) and substituted benzenes has been investigated using density functional theory (DFT), MP2, and CCSD(T)/CBS methods. The results derived from these calculations revealed predominant non-covalent π⋯ClC₂H interactions in all cases. The predicted interaction energies for substituted benzene/ClC₂H complexes span a narrow range from -1.61 to -3.96 kcal/mol, indicating that the π⋯ClC₂H interaction is comparable in strength to well-documented C-H⋯π interactions. The trend for interaction energies was found to be hexafluorobenzene-ClC₂H < sym-tetrafluorobenzene- ClC₂H < sym-trifluorobenzene-ClC₂H < sym-difluorobenzene-ClC₂H < benzene-ClC₂H < sym-dimethylbenzene-ClC₂H < sym-trimethylbenzene-ClC₂H < sym-tetramethylbenzene-ClC₂H < hexamethylbenzene-ClC ₂H. We have shown that electron-withdrawing groups weaken the complex, whereas electron-donating groups strengthen the interaction energy of the complex.

Original language	English
Pages (from-to)	16-21
Number of pages	6
Journal	Chemical Physics Letters
Volume	602
DOIs	https://doi.org/10.1016/j.cplett.2014.04.010
State	Published - 20 May 2014

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@article{e41783c3663642e181a8aa4b2fba0b96,

title = "Tuning the C-X⋯π interaction of benzene-chloroacetylene complexes by aromatic substitutions",

abstract = "The interaction between chloroacetylene (C2HCl) and substituted benzenes has been investigated using density functional theory (DFT), MP2, and CCSD(T)/CBS methods. The results derived from these calculations revealed predominant non-covalent π⋯ClC2H interactions in all cases. The predicted interaction energies for substituted benzene/ClC2H complexes span a narrow range from -1.61 to -3.96 kcal/mol, indicating that the π⋯ClC2H interaction is comparable in strength to well-documented C-H⋯π interactions. The trend for interaction energies was found to be hexafluorobenzene-ClC2H < sym-tetrafluorobenzene- ClC2H < sym-trifluorobenzene-ClC2H < sym-difluorobenzene-ClC2H < benzene-ClC2H < sym-dimethylbenzene-ClC2H < sym-trimethylbenzene-ClC2H < sym-tetramethylbenzene-ClC2H < hexamethylbenzene-ClC 2H. We have shown that electron-withdrawing groups weaken the complex, whereas electron-donating groups strengthen the interaction energy of the complex.",

author = "S. Karthikeyan and Lee, \{Jin Yong\}",

year = "2014",

month = may,

day = "20",

doi = "10.1016/j.cplett.2014.04.010",

language = "English",

volume = "602",

pages = "16--21",

journal = "Chemical Physics Letters",

issn = "0009-2614",

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T1 - Tuning the C-X⋯π interaction of benzene-chloroacetylene complexes by aromatic substitutions

AU - Karthikeyan, S.

AU - Lee, Jin Yong

PY - 2014/5/20

Y1 - 2014/5/20

N2 - The interaction between chloroacetylene (C2HCl) and substituted benzenes has been investigated using density functional theory (DFT), MP2, and CCSD(T)/CBS methods. The results derived from these calculations revealed predominant non-covalent π⋯ClC2H interactions in all cases. The predicted interaction energies for substituted benzene/ClC2H complexes span a narrow range from -1.61 to -3.96 kcal/mol, indicating that the π⋯ClC2H interaction is comparable in strength to well-documented C-H⋯π interactions. The trend for interaction energies was found to be hexafluorobenzene-ClC2H < sym-tetrafluorobenzene- ClC2H < sym-trifluorobenzene-ClC2H < sym-difluorobenzene-ClC2H < benzene-ClC2H < sym-dimethylbenzene-ClC2H < sym-trimethylbenzene-ClC2H < sym-tetramethylbenzene-ClC2H < hexamethylbenzene-ClC 2H. We have shown that electron-withdrawing groups weaken the complex, whereas electron-donating groups strengthen the interaction energy of the complex.

AB - The interaction between chloroacetylene (C2HCl) and substituted benzenes has been investigated using density functional theory (DFT), MP2, and CCSD(T)/CBS methods. The results derived from these calculations revealed predominant non-covalent π⋯ClC2H interactions in all cases. The predicted interaction energies for substituted benzene/ClC2H complexes span a narrow range from -1.61 to -3.96 kcal/mol, indicating that the π⋯ClC2H interaction is comparable in strength to well-documented C-H⋯π interactions. The trend for interaction energies was found to be hexafluorobenzene-ClC2H < sym-tetrafluorobenzene- ClC2H < sym-trifluorobenzene-ClC2H < sym-difluorobenzene-ClC2H < benzene-ClC2H < sym-dimethylbenzene-ClC2H < sym-trimethylbenzene-ClC2H < sym-tetramethylbenzene-ClC2H < hexamethylbenzene-ClC 2H. We have shown that electron-withdrawing groups weaken the complex, whereas electron-donating groups strengthen the interaction energy of the complex.

UR - https://www.scopus.com/pages/publications/84899820690

U2 - 10.1016/j.cplett.2014.04.010

DO - 10.1016/j.cplett.2014.04.010

M3 - Article

AN - SCOPUS:84899820690

SN - 0009-2614

VL - 602

SP - 16

EP - 21

JO - Chemical Physics Letters

JF - Chemical Physics Letters

ER -

Tuning the C-X⋯π interaction of benzene-chloroacetylene complexes by aromatic substitutions

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