Effects of Rapid Intramolecular Electron Transfer on Vibrational Spectra-Reference-Cited by-同舟云学术

Effects of Rapid Intramolecular Electron Transfer on Vibrational Spectra

Published:1997-08 Issue:5326 Volume:277 Page:660-663
ISSN:0036-8075
Container-title:Science
language:en
Short-container-title:Science

Author:

Ito Tasuku¹²,Hamaguchi Tomohiko¹²,Nagino Haruko¹²,Yamaguchi Tadashi¹²,Washington John¹²,Kubiak Clifford P.¹²

Affiliation:

1. T. Ito, T. Hamaguchi, H. Nagino, T. Yamaguchi, Department of Chemistry, Tohoku University, Aoba, Aramaki, Aoba-ku, Sendai 980-77, Japan.

2. J. Washington and C. P. Kubiak, Department of Chemistry, Purdue University, West Lafayette, IN 47907–1393, USA.

Abstract

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 ν(CO) bands for clusters with rate constants for intramolecular electron transfer k e increasing from = 1 × 10 9 s – 1 up to 5 × 10 11 and 9 × 10 11 s – 1 , respectively. These data provide a strong correlation between rates of intramolecular electron transfer and infrared spectral bandshape.

Publisher

American Association for the Advancement of Science (AAAS)

Subject

Multidisciplinary

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