溶剂化
离子液体
钋
化学
氧化还原
电化学
化学物理
催化作用
离子键合
计算化学
热力学
离子
物理化学
有机化学
电极
物理
作者
Kateryna Goloviznina,Mathieu Salanne
标识
DOI:10.1021/acs.jpcb.2c07238
摘要
Redox-active organic species play an important role in catalysis, energy storage, and biotechnology. One of the representatives is the 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) radical, used as a mediator in organic synthesis and considered a safe alternative to heavy metals. In order to develop a TEMPO-based system with well-controlled electrochemical and catalytic properties, a reaction medium should be carefully chosen. Being highly conductive, stable, and low flammability fluids, ionic liquids (ILs) seem to be promising solvents with easily adjustable physical and solvation properties. In this work, we give an insight into the local structure of ILs around TEMPO and its oxidized form, TEMPO+, underlining striking differences in the solvation of these two species. The analysis is coupled with a study of thermodynamics and kinetics of oxidation in the frame of Marcus theory. Our systematic investigation includes imidazolium, pyrrolydinium, and phosphonium families combined with anions of different size, polarity, and flexibility, opting to provide a clear and comprehensive picture of the impact of the nature of IL ions on the behavior of radical/cation redox pairs. The obtained results will help to explain experimentally observed effects and to rationalize the design of TEMPO/IL systems.
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