Charge Tethering Drives Intermediate-Range Order and Slow Dynamics in Zwitterionic Liquids
Raphael Ogbodo1, Laxmi Adhikari2, Clinton Adu3
1Department of Chemistry, The University of Iowa, Iowa City, Iowa 52242, United States.
None:
We have synthesized and characterized a family of zwitterionic liquids (ZwLs) based on the poly(ethylene oxide) imidazolium cation and the alkyl sulfonate anion. To better rationalize ZwLs' structural behavior and network-forming properties, we have computationally studied them in contrast to isostructural but chemically untethered ionic liquid (IL) analogues. Perhaps surprisingly, it is the molecular liquids and not the ILs that show the most self-assembly and intermediate-range order associated with scattering prepeaks; the ZwLs display also the slowest dynamics. This is consistent with prior work showing the importance of networks in considering the viscoelastic relaxation of liquids. We find that, because of their significantly large molecular dipoles, these zwitterions are versatile network-building blocks that result in highly viscous liquids. From a structural perspective, networks in these ZwLs sit somewhere in between what would be true chemical connectivity and the Coulombic networks observed in ionic liquids.
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