Effects of Rapid Intramolecular Electron Transfer on Vibrational Spectra

摘要

Single-electron reductions of linked triruthenium clusters of the general type Ru_3-pyr-azine-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 v(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.