| Hydroxyl Ionic Liquids: The Differentiating Effect of Hydroxyl on Polarity due to Ionic Hydrogen Bonds between Hydroxyl and Anions | |
| Department | 绿色化学研究发展中心 |
Zhang SG(张世国); Qi XJ(亓秀娟) ; Ma XY(马祥元); Lu LJ(卢六斤); Deng YQ(邓友全)
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| 2010 | |
| Source Publication | J. Phys. Chem. B
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| ISSN | 1520-6106 |
| Volume | 114Pages:3912-3920 |
| Abstract | 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 anionindependent polarity with similar ET(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 (ET(30) ) 51.2-61.7 kcal/mol) and is strongly anion-dependent. According to their ET(30) or ET(33) values, the hydroxyl ILs can be further classified into the following three groups: (Ι) acetate-based hydroxyl ILs [HOEMIm][AC] exhibit polarity scale (ET(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 (ET(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” (ET(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. |
| Subject Area | 物理化学 |
| Funding Organization | the National Natural Science Foundation of China (No. 20533080) |
| Indexed By | SCI |
| Language | 英语 |
| Funding Project | 绿色催化课题 |
| Citation statistics | |
| Document Type | 期刊论文 |
| Identifier | http://ir.licp.cn/handle/362003/2206 |
| Collection | 绿色化学研究发展中心 |
| Corresponding Author | Deng YQ(邓友全) |
| Recommended Citation GB/T 7714 | Zhang SG,Qi XJ,Ma XY,et al. Hydroxyl Ionic Liquids: The Differentiating Effect of Hydroxyl on Polarity due to Ionic Hydrogen Bonds between Hydroxyl and Anions[J]. J. Phys. Chem. B,2010,114:3912-3920. |
| APA | 张世国,亓秀娟,马祥元,卢六斤,&邓友全.(2010).Hydroxyl Ionic Liquids: The Differentiating Effect of Hydroxyl on Polarity due to Ionic Hydrogen Bonds between Hydroxyl and Anions.J. Phys. Chem. B,114,3912-3920. |
| MLA | 张世国,et al."Hydroxyl Ionic Liquids: The Differentiating Effect of Hydroxyl on Polarity due to Ionic Hydrogen Bonds between Hydroxyl and Anions".J. Phys. Chem. B 114(2010):3912-3920. |
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