Influence of the Counteranion on the Ability of 1-Dodecyl-3-methyltriazolium Ionic Liquids to Form Mesophases

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• 作者：Kathrin Stappert ; Derya 脺nal ; Eike T. Spielberg ; Anja-Verena Mudring
• 刊名：Crystal Growth & Design
• 出版年：2015
• 出版时间：February 4, 2015
• 年：2015
• 卷：15
• 期：2
• 页码：752-758
• 全文大小：388K
• ISSN：1528-7505

文摘

The influence of the counteranion on the ability of the mesogenic cation 1-methyl-3-dodecyl-triazolium to form mesophases is explored. To that avail, salts of the cation with anions of different size, shape, and hydrogen bonding capability such as Cl^{鈥?/sup>, Br鈥?/sup>, I鈥?/sup>, I₃鈥?/sup>, PF₆鈥?/sup>, and Tf₂N鈥?/sup> [bis(trifluorosulfonyl)amide] were synthesized and characterized. The crystal structures of the bromide, the iodide, and the triiodide reveal that the cations form bilayers with cations oriented in opposite directions featuring interdigitated alkyl tails. Within the layers, the cations are separated by anions. The rod-shaped triiodide anion forces the triazolium cation to align with it in this crystal structure but due to its space requirement reduces the alkyl chain interdigitation which prevents the formation of a mesophase. Rather the compound transforms directly from a crystalline solid to an (ionic) liquid like the analogous bis(trifluorosulfonyl)amide. In contrast, the simple halides and the hexafluorophosphate form liquid crystalline phases. Their clearing points shift with increasing anion radius to lower temperatures.}