Nagasawa Yutaka, Miyasaka Hiroshi
Division of Frontier Materials Science, Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531, Japan.
Phys Chem Chem Phys. 2014 Jul 14;16(26):13008-26. doi: 10.1039/c3cp55465a.
Room temperature ionic liquids (ILs) are a new type of solvent with peculiar properties. ILs are usually composed of an anion and a bulky cation with one or more alkyl chains to decrease the melting point. These structural peculiarities lead to the high viscosity and the heterogeneity of ILs, which could affect chemical reactions. In the present perspective, we will first introduce the experimentally observed nature of the heterogeneous liquid structure and then introduce recent developments in the study on electron transfer (ET) and charge transfer (CT) reactions in relation with the solvation and the heterogeneity of ILs. Because of the high viscosity of ILs, diffusive solvation is expected to be slow which could be the rate-limiting factor for ET and CT processes. However, ILs could provide a unique reaction field depending on the location of the solute within the heterogeneous liquid structure and the reaction could be faster than that expected from the bulk viscosity due to the fast fluctuation of the local environment.
室温离子液体(ILs)是一类具有独特性质的新型溶剂。离子液体通常由一个阴离子和一个带有一条或多条烷基链的大体积阳离子组成,以降低熔点。这些结构特性导致了离子液体的高粘度和不均匀性,这可能会影响化学反应。在本综述中,我们将首先介绍实验观察到的非均相液体结构的性质,然后介绍与离子液体的溶剂化和不均匀性相关的电子转移(ET)和电荷转移(CT)反应研究的最新进展。由于离子液体的高粘度,扩散溶剂化预计会很慢,这可能是电子转移和电荷转移过程的速率限制因素。然而,离子液体可以根据溶质在非均相液体结构中的位置提供一个独特的反应场,并且由于局部环境的快速波动,反应可能比由本体粘度预期的要快。