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

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

Research output: Contribution to journalArticlepeer-review

21 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 languageEnglish
Pages (from-to)1926-1930
Number of pages5
JournalJournal of Physical Chemistry A
Volume114
Issue number4
Early online date31 Dec 2009
DOIs
Publication statusPublished - 4 Feb 2010

Keywords

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

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