Experimental Densities and Calculated Fractional Free Volumes of Ionic Liquids with Tri- and Tetra-substituted Imidazolium Cations
Experimental Densities and Calculated Fractional Free Volumes of Ionic Liquids with Tri- and Tetra-substituted Imidazolium Cations
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三取代和四取代咪唑鎓阳离子离子液体的实验密度和计算的自由体积
DOI：
10.1021/acs.jced.7b01033
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发表时间：
2018
影响因子：
--
通讯作者：
Bara, Jason E.
中科院分区：
文献类型：
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作者：
Yue, Shuwen;Roveda, John D.;Mittenthal, Max S.;Shannon, Matthew S.;Bara, Jason E.
尽管据估计，至少有100万种离子液体（il）可以使用商业上可获得的起始材料，但在实验合成、表征和各种应用研究中，很大一部分离子液体是围绕相对简单的1-n-烷基-3-甲基咪唑（[Cnmim]）阳离子基序构建的。然而，对于为什么三官能化或四官能化咪唑阳离子受到的关注少得多，并没有根本的限制或原因。仅存在少量三功能化咪唑基il的物理性质数据，几乎没有关于四功能化il的数据。因此，在ILs的“地图”上有一个很大程度上尚未探索的广阔实验空间。我们试图对这些“未知的水域”进行初步探索，并在咪唑环的C(2)、C(4)和/或C(5)位置(以及N（1)和N(3)）上合成了具有多个官能团的咪唑基il。本文报道了这些三官能化和四官能化il的合成和实验密度，以及COSMOTherm计算的密度和分数自由体积。据我们所知，这是有关C(4)和C(5)位置取代的il的详细实验测量或计算研究的第一份报告。
Although it has been estimated that there are at least 1 million ionic liquids (ILs) that are accessible using commercially available starting materials, a great portion of the ILs that have been experimentally synthesized, characterized, and studied in a variety of applications are built around the relatively simple 1-n-alkyl-3-methylimidazolium ([Cnmim]) cation motif. Yet, there is no fundamental limitation or reason as to why tri- or tetra-functionalized imidazolium cations have received far less attention. Scant physical property data exist for just a few trifunctionalized imidazolium-based ILs and there is virtually no data on tetra-functionalized ILs. Thus, there are a broad experimental spaces on the “map” of ILs that are largely unexplored. We have sought to make an initial expedition into these “uncharted waters” and have synthesized imidazolium-based ILs with one more functional group(s) at the C(2), C(4), and/or C(5) positions of the imidazolium ring (as well as N(1) and N(3)). This manuscript reports the synthesis and experimental densities of these tri- and tetra-functionalized ILs as well as calculated densities and fractional free volumes from COSMOTherm. To the best of our knowledge, this is the first report of any detailed experimental measurements or computational studies relating to ILs with substitutions at the C(4) and C(5) positions.