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

J Phys Chem A. 2009 Sep 24;113(38):10367-75. doi: 10.1021/jp905701p.

Authors

Xavier Lucas¹, David Quiñonero, Antonio Frontera, Pere M Deyà

Affiliation

¹ Departament de Química, Universitat de les Illes Balears, E-07122 Palma de Mallorca, Spain.

PMID: 19757849
DOI: 10.1021/jp905701p

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.

Publication types

Research Support, Non-U.S. Gov't

MeSH terms

Benzene Derivatives / chemistry*
Computer Simulation
Crystallography, X-Ray
Models, Chemical
Models, Molecular
Quantum Theory*

Substances

Benzene Derivatives