Dipolarity versus polarizability and acidity versus basicity of ionic liquids as a function of their molecular structures.
Dipolarity versus polarizability and acidity versus basicity of ionic liquids as a function of their molecular structures.
复制标题
DOI：
10.1002/chem.201304069
复制
发表时间：
2014-02
期刊：
影响因子：
--
通讯作者：
Alexander Schade;Nicole Behme;S. Spange
中科院分区：
文献类型：
--
作者：
Alexander Schade;Nicole Behme;S. Spange
采用溶剂化显色法测定了64种离子液体（IL）的溶剂酸性（SA）、溶剂碱性（SB）、溶剂极化率（SP）和溶剂偶极性（SdP）4个经验极性参数。SA参数仅通过使用[Fe（II）（1，10-菲咯啉）2（CN）2]（Fe），通过使用结构上可比较的染料对3-（4-氨基-3-甲基苯基）-7-苯基苯并[1，2-B：4，5-b ']二呋喃-2，6-二酮（ABF）和3-（4-N，N-二甲基氨基苯基）-7-苯基苯并[1，2-B：4，5-b ']-二呋喃-2，6-二酮（DMe-ABF），并通过使用4-叔丁基-2-（二氰基亚甲基）-5-[4-（二乙基氨基）亚苄基]-Δ（3）-噻唑啉（Th）和2-[4-（N，N-二甲基氨基）亚苄基]丙二腈（BMN）。首次对64种离子液体的SP和SdP进行了分离。与离子液体阴离子电离势相关的物理化学数据以及理论数据的相关分析表明了所用方法的正确性。发现的Catalán参数相互之间的相关性和与1-烷基-3-甲基咪唑类离子液体的烷基链长度提供了新的信息离子液体内的相互作用。确定的Catalán参数与所建立的Kamlet-Taft参数和Gutmann受体和供体数的分析比较。
The four empirical solvent polarity parameters according to the Catalán scale--solvent acidity (SA), solvent basicity (SB), solvent polarizability (SP), and solvent dipolarity (SdP)--of 64 ionic liquids (ILs) were determined by the solvatochromic method. The SA parameter was determined solely by using [Fe(II)(1,10-phenanthroline)2(CN)2] (Fe), the SB parameter by using the pair of structurally comparable dyes 3-(4-amino-3-methylphenyl)-7-phenylbenzo[1,2-b:4,5-b']difuran-2,6-dione (ABF) and 3-(4-N,N-dimethylaminophenyl)-7-phenylbenzo[1,2-b:4,5-b']-difuran-2,6-dione (DMe-ABF), and the SP and SdP parameters by using the homomorphic pair of 4-tert-butyl-2-(dicyanomethylene)-5-[4-(diethylamino)benzylidene]-Δ(3)-thiazoline (Th) and 2-[4-(N,N-dimethylamino)benzylidene]malononitrile (BMN). The separation of SP and SdP for a set of 64 various ILs was performed for the first time. Correlation analyses of SP with physicochemical data related to ionization potentials of anions of ILs as well as with theoretical data show the correctness of the applied method. The found correlations of the Catalán parameters with each other and with the alkyl-chain length of 1-alkyl-3-methylimidazolium-type ILs gives new information about interactions within ILs. An analytical comparison of the determined Catalán parameters with the established Kamlet-Taft parameters and the Gutmann acceptor and donor numbers is also presented.