Effects of rapid intramolecular electron transfer on vibrational spectra

被引：210

作者：

Ito, T ^{[1
]}

Hamaguchi, T ^{[1
]}

Nagino, H ^{[1
]}

Yamaguchi, T ^{[1
]}

Washington, J ^{[1
]}

Kubiak, CP ^{[1
]}

机构：

[1] PURDUE UNIV,DEPT CHEM,W LAFAYETTE,IN 47907

来源：

SCIENCE | 1997年 / 277卷 / 5326期

关键词：

D O I：

10.1126/science.277.5326.660

中图分类号：

O [数理科学和化学]; P [天文学、地球科学]; Q [生物科学]; N [自然科学总论];

学科分类号：

07 ; 0710 ; 09 ;

摘要：

Single-electron reductions of linked triruthenium clusters of the general type Ru-3-pyrazine-Ru-3 produced mixed valence systems showing spectroscopic characteristics of rapid intramolecular electron transfer. Reflectance infrared spectroelectrochemistry was used to characterize the vibrational spectra of mixed valence systems that contained one carbon monoxide ligand on each Ru-3 cluster. Infrared spectra in the CO stretching region showed two resolved, partially coalesced, and coalesced nu(CO) bands for clusters with rate constants for intramolecular electron transfer k(e) increasing from = 1 x 10(9) s(-1) up to 5 x 10(11) and 9 x 10(11) s(-1), respectively. These data provide a strong correlation between rates of intramolecular electron transfer and infrared spectral bandshape.

引用

页码：660 / 663

页数：4

共 34 条

[1] Oxo-centered mixed-ligand triruthenium complexes having redox-active N-methyl-4,4'-bipyridinium ions (mbpy(+)). Reversible multistep electrochemical properties of [RuIII2RuII(mu(3)-O)(mu-CH3CO2)(6)(mbpy(+))(2)(CO)](2+) and [RuIII3(mu(3)-O)(mu-CH3CO2)(6)(mbpy(+))(2)(L)](3+) (L=H2O and n-heterocyclic ligands) [J].