Tailoring Phosphonium Ionic Liquids for a Liquid–Liquid Phase Transition

作者：Beibei Yao, Marian Paluch, Mateusz Dulski, Courtney Quinn, Shannon McLaughlin, Anne McGrogan, Małgorzata Swadźba‐Kwaśny, Ż. Wojnarowska · 发表于：The Journal of Physical Chemistry Letters · 年份：2023 · DOI：10.1021/acs.jpclett.3c00099 · 被引用次数：17 · 研究领域：Ionic liquids properties and applications、Electrochemical Analysis and Applications、Catalysis and Oxidation Reactions

High Resolution Image Download MS PowerPoint Slide The existence of more than one liquid state in a single-component system remains the most intriguing physical phenomenon. Herein, we explore the effect of cation self-assembly on ion dynamics in the vicinity of liquid–liquid and liquid-glass transition of tetraalkyl phosphonium ([P mmm, n ] +, m = 4, 6; n = 2–14) ionic liquids. We found that nonpolar local domains formed by 14-carbon alkyl chains are crucial in obtaining two supercooled states of different dynamics within a single ionic liquid. Although the nano-ordering, confirmed by Raman spectroscopy, still occurs for shorter alkyl chains ( m = 6, n < 14), it does not bring calorimetric evidence of LLT. Instead, it results in peculiar behavior of ion dynamics near the liquid-glass transition and 20-times smaller size of the dynamic heterogeneity compared to imidazolium ionic liquids. These results represent a crucial step toward understanding the nature of the LLT phenomenon and offer insight into the design of efficient electrolytes based on ionic liquids revealing self-assembly behavior.