Document Type

Article

Publication Version

Published Version

Publication Date

2014

Journal or Book Title

Crystal Growth & Design

Volume

14

Issue

4

First Page

1561

Last Page

1571

DOI

10.1021/cg401396n

Abstract

To determine the essential parameters for mesophase formation in imidazolium-based ionic liquids (ILs), a library of 1-alkyl-3-dodecylimidazolium bromides was synthesized, abbreviated as CnC12, where 0 ≤ n ≤ 13, as the general notion is that a dodecyl side chain would guarantee the formation of an ionic liquid crystal (ILC). All salts were fully characterized by NMR spectroscopy and mass spectrometry. Their thermal properties were recorded, and mesophase formation was assessed. An odd–even effect is observed for 5 ≤ n ≤ 10 in the temperatures of melting transitions. While the majority of this series, as expected, formed mesophases, surprisingly compounds C2C12 and C6C12 could not be classified as ILCs, the latter being a room temperature IL, while C2C12 is a crystalline solid with melting point at 37 °C. The single crystal structure of compound 1-ethyl-3-dodecylimidazolium bromide (C2C12) was successfully obtained. Remarkably, the arrangement of imidazolium cores in the structure is very complicated due to multiple nonclassical hydrogen bonds between bromide anions and imidazolium head groups. In this arrangement, neighboring imidazolium rings are forced by hydrogen bonds to form a “face-to-face” conformation. This seems to be responsible for the elimination of a mesophase. To conclude, the general view of a dodecyl chain being a functional group to generate a mesophase is not entirely valid.

Comments

Reprinted with permission from Cryst. Growth Des., 2014, 14 (4), pp 1561–1571. Copyright 2014 American Chemical Society.

Copyright Owner

American Chemical Society

Language

en

File Format

application/pdf

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