Infrared-perturbed electron transfer process of the complex fac-[ReI(CO)3(DCEB)(3DMABN)] (ReEBA); where 3DMABN is 3-dimethylaminobenzonitrile, serving as an electron donor, and DCEB is 4,4'-(dicarboxyethyl)-2,2-bipyridine, serving as an electron acceptor, has been studied by 3-pulse UV-pump – IR-pump – IR-probe spectroscopy. Photo-induced charge separation reaction in the ReEBA complex occurs with the rate constant of (10 ps)-1. Various vibrational modes in the ReEBA were excited to test how they modulate the rate of the charge separation reaction. While no significant rate modulation was observed when the cyano group stretching mode of the 3DMABN donor was excited, a sizable effect was found when the ring stretching mode of the DCEB acceptor was excited. Kinetics modeling indicates an increase of ca. 28% of the charge separation rate when vibrational excitation is present. Vibronic coupling between vibrational modes involved in the 3-pulse measurements was quantified using relaxation-assisted two-dimensional infrared spectroscopy.

Electron transfer rate modulation in a compact Re(I) donor-acceptor complex

249th National Meeting (2015)

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