Jump to main content
Jump to site search
PLANNED MAINTENANCE Close the message box

Scheduled maintenance upgrade on Thursday 4th of May 2017 from 8.00am to 9.00am (BST).

During this time our websites will be offline temporarily. If you have any questions please use the feedback button on this page. We apologise for any inconvenience this might cause and thank you for your patience.


Issue 7, 2014
Previous Article Next Article

Competitive pi interactions and hydrogen bonding within imidazolium ionic liquids

Author affiliations

Abstract

In this paper we have explored the structural and energetic landscape of potential π+–π+ stacked motifs, hydrogen-bonding arrangements and anion–π+ interactions for gas-phase ion pair (IP) conformers and IP-dimers of 1,3-dimethylimidazolium chloride, [C1C1im]Cl. We classify cation–cation ring stacking as an electron deficient π+–π+ interaction, and a competitive anion on-top IP motif as an anion–donor π+–acceptor interaction. 21 stable IP-dimers have been obtained within an energy range of 0–126 kJ mol−1. The structures have been found to exhibit a complex interplay of structural features. We have found that low energy IP-dimers are not necessarily formed from the lowest energy IP conformers. The sampled range of IP-dimers exhibits new structural forms that cannot be recovered by examining the ion-pairs alone, moreover the IP-dimers are recovering additional key features of the local liquid structure. Including dispersion is shown to impact both the relative energy ordering and the geometry of the IPs and IP-dimers, however the impact is found to be subtle and dependent on the underlying functional.

Graphical abstract: Competitive pi interactions and hydrogen bonding within imidazolium ionic liquids

Back to tab navigation
Please wait while Download options loads

Supplementary files

Publication details

The article was received on 05 Nov 2013, accepted on 23 Dec 2013 and first published on 09 Jan 2014


Article type: Paper
DOI: 10.1039/C3CP54672A
Citation: Phys. Chem. Chem. Phys., 2014,16, 3238-3253
  •   Request permissions

    Competitive pi interactions and hydrogen bonding within imidazolium ionic liquids

    R. P. Matthews, T. Welton and P. A. Hunt, Phys. Chem. Chem. Phys., 2014, 16, 3238
    DOI: 10.1039/C3CP54672A

Search articles by author