The physical significance of the Kamlet–Taft π* parameter of ionic liquids
文献情報
Nadine Weiß, Caroline H. Schmidt, Gabi Thielemann, Esther Heid, Christian Schröder, Stefan Spange
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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