Hydroxyl Ionic Liquids: The Differentiating Effect of Hydroxyl on Polarity due to Ionic Hydrogen Bonds between Hydroxyl and Anions

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• 作者：Shiguo Zhang ; Xiujuan Qi ; Xiangyuan Ma ; Liujin Lu ; Youquan Deng
• 刊名：Journal of Physical Chemistry B
• 出版年：2010
• 出版时间：March 25, 2010
• 年：2010
• 卷：114
• 期：11
• 页码：3912-3920
• 全文大小：277K
• 年卷期：v.114,no.11(March 25, 2010)
• ISSN：1520-5207

文摘

The polarity of a series of ionic liquids (ILs) based on hydroxyethyl-imidazolium moiety with various anions ([PF₆], [NTf₂], [ClO₄], [DCA], [NO₃], [AC], and [Cl]) and their corresponding nonhydroxyl ILs was investigated by solvatochromic dyes and fluorescence probe molecules. Most of the nonhydroxyl ILs exhibit anion-independent polarity with similar E_T(30) in the narrow range of 50.7−52.6 kcal/mol, except [EMIm][AC] (49.7 kcal/mol). However, the polarity of the hydroxyl ILs covers a rather wide range (E_T(30) = 51.2−61.7 kcal/mol) and is strongly anion-dependent. According to their E_T(30) or E_T(33) values, the hydroxyl ILs can be further classified into the following three groups: (Ι) acetate-based hydroxyl ILs [HOEMIm][AC] exhibit polarity scale (E_T(30) = 51.2 kcal/mol) similar to short chain alcohol and fall in the range of the nonhydroxyl ILs; (II) Hydroxyl ILs containing anions [NO₃], [DCA], and [Cl] exhibit comparable polarity (E_T(30) = 55.5−56.9 kcal/mol), moderately higher than those of their nonhydroxyl ILs; (III) Hydroxyl ILs containing anions [PF₆], [NTf₂], and [ClO₄] possess unusual “hyperpolarity” (E_T(30) = 60.3−61.7 kcal/mol) close to protic ILs and water. Kamlet−Taft parameters and density functional theory calculations indicated that the greatly expanded range of polarity of hydroxyl ILs is correlated to an intramolecular synergistic solvent effect of the ionic hydrogen-bonded HBD/HBA complexes generated by intrasolvent HBD/HBA association between the anions and the hydroxyl group on cations, wherein hydroxyl group exhibits a significant differentiating effect on the strength of H-bonding and thus the polarity. Spiropyran-merocyanine equilibrium acted as a model polarity-sensitive reaction indeed shows obviously polarity-dependent solvatochromism, photochromism, and thermal reversion in hydroxyl ILs.