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首页> 外文期刊>The journal of physical chemistry, B. Condensed matter, materials, surfaces, interfaces & biophysical >Empirical Parameters for Solvent Acidity, Basicity, Dipolarity, and Polarizability of the Ionic Liquids [BMIM][BF4] and [BMIM][PF6]
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Empirical Parameters for Solvent Acidity, Basicity, Dipolarity, and Polarizability of the Ionic Liquids [BMIM][BF4] and [BMIM][PF6]

机译：离子液体[BMIM] [BF4]和[BMIM] [PF6]的溶剂酸度，碱性，偶极性和极化率的经验参数

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摘要

The empirical solvent scales for polarizability (SP), dipolarity (SdP), acidity (SA), and basicity (SB) have been successfully used to interpret the solvatochromism of compounds dissolved in organic solvents and their solvent mixtures. Providing that the published solvatochromic parameters for the ionic liquids 1-(1-butyl)-3-methylimidazolium tetrafluoroborate, [BMIM][BF4] and 1-(1-butyl)-3-methylimidazolium hexafluorophosphate, [BMIM][PF6], are excessively widespread, their SP, SdP, SA, and SB values are measured herein at temperatures from 293 to 353 K. Four key points are emphasized herein: (i) the origin of the solvatochromic solvent scales -the gas phase, that is the absence of any medium perturbation-; (ii) the separation of the polarizability and dipolarity effects; (iii) the simplification of the probing process in order to obtain the solvatochromic parameters; and (iv) the SP, SdP, SA, and SB solvent scales can probe the polarizability, dipolarity, acidity, and basicity of ionic liquids as well as of organic solvents and water-organic solvent mixtures. From the multiparameter approach using the four pure solvent scales one can draw the conclusion that (a) the solvent influence of [BMIM][BF4] parallels that of formamide at 293 K, both of them miscible with water; (b) [BMIM][PF6] shows a set of solvatochromic parameters similar to that of chloroacetonitrile, both of them water insoluble; and (c) that the corresponding solvent acidity and basicity of the ionic liquids can be explained to a great extent from the cation species by comparing the empirical parameters of [BMIM](+) with those of the solvent 1-methylimidazole. The insolubility of [BMIM][PF6] in water as compared to [BMIM][BF4] is tentatively connected to some extent to the larger molar volume of the anion [PF6](-), and to the difference in basicity of [PF6](-) and [BF4](-).
机译：极化率（SP），偶极性（SdP），酸度（SA）和碱度（SB）的经验溶剂规模已成功用于解释溶解在有机溶剂及其溶剂混合物中的化合物的溶剂溶变色现象。提供离子液体四氟硼酸1-（1-丁基）-3-甲基咪唑鎓[BMIM] [BF4]和六氟磷酸1-（1-丁基）-3-甲基咪唑鎓[BMIM] [PF6]的已公布溶剂化变色参数，由于它们的SP，SdP，SA和SB值过于广泛，因此在293至353 K的温度下进行测量。此处强调四个要点：（i）溶剂化变色溶剂垢的起源-气相，即没有任何介质干扰; （ii）分离极化性和偶极性效应; （iii）简化探测过程以获得溶剂变色参数; （iv）SP，SdP，SA和SB溶剂秤可以探测离子液体以及有机溶剂和水-有机溶剂混合物的极化率，偶极性，酸性和碱性。从使用四种纯溶剂标度的多参数方法可以得出以下结论：（a）[BMIM] [BF4]的溶剂影响与在293 K下与甲酰胺的溶剂影响平行，两者均与水混溶; （b）[BMIM] [PF6]显示一组类似于氯乙腈的溶剂变色参数，它们都不溶于水; （c）通过比较[BMIM]（+）的经验参数和溶剂1-甲基咪唑的经验参数，可以从阳离子种类上很大程度上解释离子液体的相应溶剂酸度和碱度。与[BMIM] [BF4]相比，[BMIM] [PF6]在水中的不溶性在某种程度上与阴离子[PF6]（-）的较大摩尔体积以及[PF6]碱度的不同暂时相关。 ]（-）和[BF4]（-）。

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