Ultrafast solvation dynamics and charge transfer reactions in room temperature ionic liquids

被引:37
作者
Nagasawa, Yutaka [1 ,2 ,3 ]
Miyasaka, Hiroshi [1 ,2 ]
机构
[1] Osaka Univ, Grad Sch Engn Sci, Dept Mat Engn Sci, Div Frontier Mat Sci, Toyonaka, Osaka 5608531, Japan
[2] Osaka Univ, Ctr Quantum Sci & Technol Extreme Condit, Toyonaka, Osaka 5608531, Japan
[3] Japan Sci & Technol Agcy JST, PRESTO, Kawaguchi, Saitama 3320012, Japan
基金
日本科学技术振兴机构;
关键词
INTRAMOLECULAR ELECTRON-TRANSFER; ECHO PEAK SHIFT; WAVELENGTH-DEPENDENT FLUORESCENCE; KERR-EFFECT SPECTRA; SOLUTE-SOLVENT INTERACTION; PROTON-TRANSFER REACTION; EXCITED-STATE DYNAMICS; ALKYL CHAIN-LENGTH; MOLECULAR-DYNAMICS; PHOTON-ECHO;
D O I
10.1039/c3cp55465a
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
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.
引用
收藏
页码:13008 / 13026
页数:19
相关论文
共 208 条
[31]   HYDROGEN-BONDING IN IMIDAZOLIUM SALTS AND ITS IMPLICATIONS FOR AMBIENT-TEMPERATURE HALOGENOALUMINATE(III) IONIC LIQUIDS [J].
ELAIWI, A ;
HITCHCOCK, PB ;
SEDDON, KR ;
SRINIVASAN, N ;
TAN, YM ;
WELTON, T ;
ZORA, JA .
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1995, (21) :3467-3472
[32]   Physical chemistry of ionic liquids [J].
Endres, Frank .
PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 2010, 12 (08) :1648-1648
[33]   Chromophore-solvent dynamics [J].
Fleming, GR ;
Cho, MH .
ANNUAL REVIEW OF PHYSICAL CHEMISTRY, 1996, 47 :109-134
[34]   Dynamics in Organic Ionic Liquids in Distinct Regions Using Charged and Uncharged Orientational Relaxation Probes [J].
Fruchey, Kendall ;
Fayer, M. D. .
JOURNAL OF PHYSICAL CHEMISTRY B, 2010, 114 (08) :2840-2845
[35]   Fluorescence probing of temperature-dependent dynamics and friction in ionic liquid local environments [J].
Funston, Alison M. ;
Fadeeva, Tatiana A. ;
Wishart, James F. ;
Castner, Edward W., Jr. .
JOURNAL OF PHYSICAL CHEMISTRY B, 2007, 111 (18) :4963-4977
[36]   Ionic liquids as electrolytes [J].
Galinski, Maciej ;
Lewandowski, Andrzej ;
Stepniak, Izabela .
ELECTROCHIMICA ACTA, 2006, 51 (26) :5567-5580
[37]   Three-pulse photon echo peak shift spectroscopy as a probe of flexibility and conformational heterogeneity in protein folding [J].
Gibson, Emily A. ;
Shen, Zhaochuan ;
Jimenez, Ralph .
CHEMICAL PHYSICS LETTERS, 2009, 473 (4-6) :330-335
[38]   The effects of anion and cation substitution on the ultrafast solvent dynamics of ionic liquids: A time-resolved optical Kerr-effect spectroscopic study [J].
Giraud, G ;
Gordon, CM ;
Dunkin, IR ;
Wynne, K .
JOURNAL OF CHEMICAL PHYSICS, 2003, 119 (01) :464-477
[39]   New developments in catalysis using ionic liquids [J].
Gordon, CM .
APPLIED CATALYSIS A-GENERAL, 2001, 222 (1-2) :101-117
[40]   Two-state model for the photophysics of 9,9′-bianthryl.: Fluorescence, transient-absorption, and semiempirical studies [J].
Grabner, G ;
Rechthaler, K ;
Köhler, G .
JOURNAL OF PHYSICAL CHEMISTRY A, 1998, 102 (04) :689-696