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Issue 7, 2014
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Competitive pi interactions and hydrogen bonding within imidazolium ionic liquids

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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

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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
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    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

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