Preparation, Properties, and Crystal Structures of Organometallic Ionic Liquids Comprising 1-Ferrocenyl-3-alkylimidazolium-Based Salts of Bis(trifluoromethanesulfonyl)amide and Hexafluorophosphate
Preparation, Properties, and Crystal Structures of Organometallic Ionic Liquids Comprising 1-Ferrocenyl-3-alkylimidazolium-Based Salts of Bis(trifluoromethanesulfonyl)amide and Hexafluorophosphate
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DOI：
10.1021/ic1013363
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发表时间：
2010-11-01
影响因子：
4.6
通讯作者：
Mochida, Tomoyuki
中科院分区：
文献类型：
--
作者：
Miura, Yuji;Shimizu, Fumiko;Mochida, Tomoyuki
合成了1-二茂铁基-3-烷基咪唑的双（三氟甲磺酰基）酰胺（TFSA）、六氟磷酸盐（PF 6-）和碘化物盐，并研究了它们的热物理性质，包括对烷基链长（甲基十六烷基）的依赖性. TFSA盐是高粘度的离子液体，熔点在室温左右。还制备了1-二茂铁基-4-甲基三唑鎓盐用于比较。二茂铁基咪唑和二茂铁基三唑阳离子的二茂铁基部分和唑部分的氧化还原波，并表现出相应的电荷转移带在330 nm左右，这是使用Marcus-Hush模型进行分析。在低温下的晶体结构测定表明，PF 6-和碘化物盐形成层状结构组成的离子层的带电部分。TFSA盐在阳离子的氢原子和阴离子的氧原子之间表现出短的氢键状分子间接触。
Bis(trifluoromethanesulfonyl)amide (TFSA), hexafluorophosphate (PF6-), and iodide salts of 1-ferrocenyl-3-alkylimidazolium were prepared and their thermal and physical properties, including the dependence on alkyl chain length (methyl hexadecyl), were investigated. The TFSA salts were highly viscous ionic liquids with melting points around room temperature. 1-Ferrocenyl-4-methyltriazolium salts were also prepared for comparison. The ferrocenylimidazolium and ferrocenyltriazolium cations showed redox waves for both the ferrocenyl moiety and the azolium moiety and exhibited corresponding charge-transfer bands at around 330 nm, which were analyzed using the Marcus-Hush model. Crystal structure determinations at low temperature revealed that the PF6- and iodide salts form layerlike structures composed of ionic layers of the charged moieties. The TFSA salt exhibited short hydrogen-bond-like intermolecular contacts between the hydrogen atoms of the cation and oxygen atoms of the anion.