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Science 1 August 1997:
Vol. 277. no. 5326, pp. 660 - 663
DOI: 10.1126/science.277.5326.660
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Reports

Effects of Rapid Intramolecular Electron Transfer on Vibrational Spectra

Tasuku Ito, * Tomohiko Hamaguchi, Haruko Nagino, Tadashi Yamaguchi, John Washington, Clifford P. Kubiak *

Single-electron reductions of linked triruthenium clusters of the general type Ru3-pyrazine-Ru3 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 Ru3 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 ke increasing from = 1 × 109 s-1 up to 5 × 1011 and 9 × 1011 s-1, respectively. These data provide a strong correlation between rates of intramolecular electron transfer and infrared spectral bandshape.

T. Ito, T. Hamaguchi, H. Nagino, T. Yamaguchi, Department of Chemistry, Tohoku University, Aoba, Aramaki, Aoba-ku, Sendai 980-77, Japan.
J. Washington and C. P. Kubiak, Department of Chemistry, Purdue University, West Lafayette, IN 47907-1393, USA.
*   To whom correspondence should be addressed. E-mail: ito{at}agnus.chem.tohoku.ac.jp and cliff{at}cv3.chem.purdue.edu

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