Ionic Liquids under Radiation and the Dimer Radical Dicyanamide Anion

作者：Hung H. Nguyen, Katie Huber, Dhanjit Das, James F. Wishart, David A. Blank, Claudio J. Margulis · 发表于：The Journal of Physical Chemistry B · 年份：2025 · DOI：10.1021/acs.jpcb.5c07381 · 被引用次数：1 · 研究领域：Ionic liquids properties and applications、Electrohydrodynamics and Fluid Dynamics、Photochemistry and Electron Transfer Studies

High Resolution Image Download MS PowerPoint Slide Ionic liquids (ILs) used in solar, electrochemical, nuclear, or even space exploration applications will necessarily be exposed to conditions in which electron detachment may occur and transient charge-depleted radical species may form. In a recent article ( J. Am. Chem. Soc. 2025, 147, 23395–23398), we studied the different possible kinetic fates of an excess electron in the popular 1-butyl-1-methylpyrrolidinium dicyanamide IL but did not address the nature of electron-deficient transient radical species these leaving electrons produce, the so-called holes. Using pulse radiolysis measurements and first-principles calculations in the bulk and gas phases to interpret these, we show that the most likely hole species in this IL is a dimer radical anion that, somewhat surprisingly, has similar spectral features to the excess electron, including a broad near-infrared absorption band.