A Pseudo Hydronium Solvate Ionic Liquid and Taxonomy of the Allied Protic Media

拟水合氢离子液体及其相关质子介质的分类

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Abstract

A ternary equimolar mixture of water, 18-crown-6-ether (18C6), and (+)-10-camphorsulfonic acid (CSA), [H(2)O]/[18C6]/[CSA] = 1/1/1 by mole, has been prepared and characterized as a "pseudo hydronium solvate ionic liquid (IL)." In this system, 18C6-coordinated water is only partially protonated by CSA, resulting in a coexistence of 18C6-solvated hydronium (H(3)O(+)) ions and neutral [H(2)O·18C6] complexes. Unlike previously reported protic media formed with superacids, which undergo complete proton transfer to form solvate ILs, this system retains a significant fraction of neutral species due to the moderate ΔpK(a) between CSA and water. Spectroscopic measurements including diffusion coefficient assessments reveal that proton transport proceeds via a Grotthuss-like mechanism involving neutral complexes, distinguishing this medium from both vehicle-type and fast-proton-diffusive solvate ILs. Analysis using dimensionless parameters-self-diffusion coefficient and molar conductivity ratios-offers a quantitative framework for profiling ionicity and transport behavior in such systems. These findings provide fundamental insights into proton conduction mechanisms in pseudo-ionic environments and establish a rational basis for designing new proton-conducting materials. The chiral nature of the CSA(-) anion further expands the potential of this system for applications in asymmetric catalysis, electrochemical sensing, and photoelectrochemical energy conversion devices.

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