The physical significance of the Kamlet-Taft π* parameter of ionic liquids.

The physical significance of the Kamlet-Taft π* parameter of ionic liquids.
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离子液体Kamlet-Taft Ï*参数的物理意义

DOI:
10.1039/d0cp04989a
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发表时间:
2021
期刊:
Physical chemistry chemical physics : PCCP
影响因子:
--
通讯作者:
S. Spange
S. Spange
中科院分区:
--
文献类型:
--
作者:
N. Weiß;C. H. Schmidt;G. Thielemann;E. Heid;C. Schröder;S. Spange

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以4-叔丁基-2-((二氰亚甲基)-5-[4-N,N-二乙氨基)-亚苄基]-3-噻唑啉和5-(N,N-二甲氨基)-5‘-硝基-2,2’-联噻吩作溶剂变色探针,测定了不同离子液体的Kamlet-Taft偶极/极化率参数π*。与已建立的π*探针N,N-二乙基硝基苯胺相比,本文提出的生色团与利用129Xe的化学位移进行的极性测量显示出很好的一致性。它们不会因为氢键导致某些离子液体的π*值过高而产生额外的紫外光/可见光漂移。结合大量不同的离子液体,这些新的发色团因此可以详细分析π*的物理意义,并与量子力学方法进行比较。我们发现π*与摩尔折射率与摩尔体积的比率密切相关,从而与折射率密切相关。
The Kamlet–Taft dipolarity/polarizability parameters π* for various ionic liquids were determined using 4-tert-butyl-2-((dicyanomethylene)-5-[4-N,N-diethylamino)-benzylidene]-Δ3-thiazoline and 5-(N,N-dimethylamino)-5′-nitro-2,2′-bithiophene as solvatochromic probes. In contrast to the established π*-probe N,N-diethylnitroaniline, the chromophores presented here show excellent agreement with polarity measurement using the chemical shift of 129Xe. They do not suffer from additional bathochromic UV/vis shifts caused by hydrogen-bonding resulting in too high π*-values for some ionic liquids. In combination with large sets of various ionic liquids, these new chromophores thereby allow for detailed analysis of the physical significance of π* and the comparison to quantum-mechanical methods. We find that π* correlates strongly with the ratio of molar refractivity to molar volume, and thus with the refractive index.
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