Substituent effects in ion-pi interactions: fine-tuning via the ethynyl group

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

doi:10.1021/jp9089672

Substituent effects in ion-pi interactions: fine-tuning via the ethynyl group

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

Biological Chemistry and Drug Discovery

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

23 Citations (Scopus)

Abstract

In this work, we report a high level theoretical study (RI-MP2(full)/aug-cc-pVDZ) that deals with the effect of electron-withdrawing substituents on cation-pi and anion-pi interactions in the absence/presence of triple bonds between the substituent and the aromatic ring. The ethynyl group is able to finely tune the interaction energy of the complexes. Interestingly, for the cation-pi complexes, it reduces the effect of the electron withdrawing groups (EWG), improving the interaction. For anion-pi complexes, it boosts the effect of the EWG, improving the interaction as well. This dual behavior has been studied by examining the geometric and energetic features of the complexes, "atoms-in-molecules" analysis and charge transfer effects.

Original language	English
Pages (from-to)	1926-1930
Number of pages	5
Journal	Journal of Physical Chemistry A
Volume	114
Issue number	4
Early online date	31 Dec 2009
DOIs	https://doi.org/10.1021/jp9089672
Publication status	Published - 4 Feb 2010

Keywords

Ethylenes
Models, Molecular
Molecular structure
Thermodynamics
Journal article
Research support, Non-U.S. Gov't

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10.1021/jp9089672

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title = "Substituent effects in ion-pi interactions: fine-tuning via the ethynyl group",

abstract = "In this work, we report a high level theoretical study (RI-MP2(full)/aug-cc-pVDZ) that deals with the effect of electron-withdrawing substituents on cation-pi and anion-pi interactions in the absence/presence of triple bonds between the substituent and the aromatic ring. The ethynyl group is able to finely tune the interaction energy of the complexes. Interestingly, for the cation-pi complexes, it reduces the effect of the electron withdrawing groups (EWG), improving the interaction. For anion-pi complexes, it boosts the effect of the EWG, improving the interaction as well. This dual behavior has been studied by examining the geometric and energetic features of the complexes, {"}atoms-in-molecules{"} analysis and charge transfer effects.",

keywords = "Ethylenes, Models, Molecular, Molecular structure, Thermodynamics, Journal article, Research support, Non-U.S. Gov't",

author = "Xavier Lucas and Antonio Frontera and David Qui{\~n}onero and Dey{\`a}, \{Pere M.\}",

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TY - JOUR

T1 - Substituent effects in ion-pi interactions

T2 - fine-tuning via the ethynyl group

AU - Lucas, Xavier

AU - Frontera, Antonio

AU - Quiñonero, David

AU - Deyà, Pere M.

PY - 2010/2/4

Y1 - 2010/2/4

N2 - In this work, we report a high level theoretical study (RI-MP2(full)/aug-cc-pVDZ) that deals with the effect of electron-withdrawing substituents on cation-pi and anion-pi interactions in the absence/presence of triple bonds between the substituent and the aromatic ring. The ethynyl group is able to finely tune the interaction energy of the complexes. Interestingly, for the cation-pi complexes, it reduces the effect of the electron withdrawing groups (EWG), improving the interaction. For anion-pi complexes, it boosts the effect of the EWG, improving the interaction as well. This dual behavior has been studied by examining the geometric and energetic features of the complexes, "atoms-in-molecules" analysis and charge transfer effects.

AB - In this work, we report a high level theoretical study (RI-MP2(full)/aug-cc-pVDZ) that deals with the effect of electron-withdrawing substituents on cation-pi and anion-pi interactions in the absence/presence of triple bonds between the substituent and the aromatic ring. The ethynyl group is able to finely tune the interaction energy of the complexes. Interestingly, for the cation-pi complexes, it reduces the effect of the electron withdrawing groups (EWG), improving the interaction. For anion-pi complexes, it boosts the effect of the EWG, improving the interaction as well. This dual behavior has been studied by examining the geometric and energetic features of the complexes, "atoms-in-molecules" analysis and charge transfer effects.

KW - Ethylenes

KW - Models, Molecular

KW - Molecular structure

KW - Thermodynamics

KW - Journal article

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

U2 - 10.1021/jp9089672

DO - 10.1021/jp9089672

M3 - Article

C2 - 20043658

SN - 1089-5639

VL - 114

SP - 1926

EP - 1930

JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

IS - 4

ER -

Substituent effects in ion-pi interactions: fine-tuning via the ethynyl group

Abstract

Keywords

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