Solvent dynamical control of electron-transfer rates in mixed-valence complexes observed by infrared spectral line shape coalescence

被引：65

作者：

Londergan, CH ^{[1
]}

Salsman, JC ^{[1
]}

Ronco, S ^{[1
]}

Dolkas, LM ^{[1
]}

Kubiak, CP ^{[1
]}

机构：

[1] Univ Calif San Diego, Dept Biochem & Chem, La Jolla, CA 92093 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2002年 / 124卷 / 22期

关键词：

D O I：

10.1021/ja0202356

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Rate constants for intramolecular electron transfer within the intervalence charge transfer (-1) states of the complexes [{Ru3O(OAc)6(L)(CO)}2(μ-pz)] (where L= 4-(dimethylamino)pyridine (1), pyridine (2), 3-cyanopyridine (3), or 4-cyanopyridine (4) and pz = pyrazine) were determined by coalescence of infrared (IR) vibrational spectral line shapes in seven solvents. The electron-transfer times (kET-1) show a strong correlation with solvent relaxation times determined in separate ultrafast time-resolved fluorescence experiments. The best comparison is found with the parameter t1e, which is ascribed to inertial solvent relaxation. The IR spectra of these mixed-valence complexes are thus a steady-state spectral probe of ultrafast, dynamic solvent relaxation processes which are otherwise only accessible using laser-pumped, ultrafast time-resolved measurements. Copyright © 2002 American Chemical Society.

引用

页码：6236 / 6237

页数：2

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