Electrochemically induced electron transfer through molecular bridges

In this Opinion, we address some of the most important results obtained electrochemically in the area of intramolecular electron transfer (ET). The focus is on freely diffusing molecular systems in which a donor D and an acceptor A are separated by a well-defined bridge B (D-B-A systems). B can be a saturated spacer, a delocalized bridge, or the more complex peptide backbones. As to the acceptors, the selected examples encompass species that can be charged reversibly but a special emphasis is on ETs associated with the concerted cleavage of a sigma bond (dissociative ETs). Our goal is to showcase the essential background, the most appropriate electrochemical tools and methodologies, and a series of selected examples where molecular electrochemistry has provided invaluable information on the mechanisms of intramolecular ET and electronic communication through bridges.