Counterintuitive substituent effect of the ethynyl group in ion-pi interactions

Xavier Lucas; David Quiñonero; Antonio Frontera; Pere M. Deyà

doi:10.1021/jp905701p

Counterintuitive substituent effect of the ethynyl group in ion-pi interactions

Xavier Lucas, David Quiñonero, Antonio Frontera (Lead / Corresponding author), Pere M. Deyà (Lead / Corresponding author)

Biological Chemistry and Drug Discovery

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

42 Citations (Scopus)

Abstract

In this article, we report a high-level theoretical study (SCS-RI-MP2(full)/aug-cc-pVTZ) that deals with the substituent effect of the ethynyl group on ion-pi interactions in 1,3,5-triethynylbenzene systems. The ethynyl group is able to act as an electron-withdrawing group, thus favoring the anion-pi interaction. Unexpectedly, it has little influence on the cation-pi interaction. This behavior has been studied by examining the geometrical and energetic features of the complexes, AIM, and charge analyses and partitioning the interaction energy. The simultaneous interaction of 1,3,5-triethynylbenzene with cations and anions by opposite sides of the ring has also been studied.

Original language	English
Pages (from-to)	10367-10375
Number of pages	9
Journal	Journal of Physical Chemistry A
Volume	113
Issue number	38
Early online date	27 Aug 2009
DOIs	https://doi.org/10.1021/jp905701p
Publication status	Published - 24 Sept 2009

Keywords

Benzene derivatives
Computer simulation
Crystallography, X-Ray
Models, Chemical
Models, Molecular
Quantum theory
Journal article
Research support, Non-U.S. Gov't

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10.1021/jp905701p

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title = "Counterintuitive substituent effect of the ethynyl group in ion-pi interactions",

abstract = "In this article, we report a high-level theoretical study (SCS-RI-MP2(full)/aug-cc-pVTZ) that deals with the substituent effect of the ethynyl group on ion-pi interactions in 1,3,5-triethynylbenzene systems. The ethynyl group is able to act as an electron-withdrawing group, thus favoring the anion-pi interaction. Unexpectedly, it has little influence on the cation-pi interaction. This behavior has been studied by examining the geometrical and energetic features of the complexes, AIM, and charge analyses and partitioning the interaction energy. The simultaneous interaction of 1,3,5-triethynylbenzene with cations and anions by opposite sides of the ring has also been studied.",

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T1 - Counterintuitive substituent effect of the ethynyl group in ion-pi interactions

AU - Lucas, Xavier

AU - Quiñonero, David

AU - Frontera, Antonio

AU - Deyà, Pere M.

PY - 2009/9/24

Y1 - 2009/9/24

N2 - In this article, we report a high-level theoretical study (SCS-RI-MP2(full)/aug-cc-pVTZ) that deals with the substituent effect of the ethynyl group on ion-pi interactions in 1,3,5-triethynylbenzene systems. The ethynyl group is able to act as an electron-withdrawing group, thus favoring the anion-pi interaction. Unexpectedly, it has little influence on the cation-pi interaction. This behavior has been studied by examining the geometrical and energetic features of the complexes, AIM, and charge analyses and partitioning the interaction energy. The simultaneous interaction of 1,3,5-triethynylbenzene with cations and anions by opposite sides of the ring has also been studied.

AB - In this article, we report a high-level theoretical study (SCS-RI-MP2(full)/aug-cc-pVTZ) that deals with the substituent effect of the ethynyl group on ion-pi interactions in 1,3,5-triethynylbenzene systems. The ethynyl group is able to act as an electron-withdrawing group, thus favoring the anion-pi interaction. Unexpectedly, it has little influence on the cation-pi interaction. This behavior has been studied by examining the geometrical and energetic features of the complexes, AIM, and charge analyses and partitioning the interaction energy. The simultaneous interaction of 1,3,5-triethynylbenzene with cations and anions by opposite sides of the ring has also been studied.

KW - Benzene derivatives

KW - Computer simulation

KW - Crystallography, X-Ray

KW - Models, Chemical

KW - Models, Molecular

KW - Quantum theory

KW - Journal article

KW - Research support, Non-U.S. Gov't

U2 - 10.1021/jp905701p

DO - 10.1021/jp905701p

M3 - Article

C2 - 19757849

SN - 1089-5639

VL - 113

SP - 10367

EP - 10375

JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

IS - 38

ER -

Counterintuitive substituent effect of the ethynyl group in ion-pi interactions

Abstract

Keywords

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