Anion-regulated electronic communication in a cyclometalated diruthenium complex with a urea bridge

A combined study of electrochemical measurements, intervalence charge transfer analysis, and DFT calculations suggests that the degree of urea-mediated electronic coupling between two cyclometalated ruthenium sites is enhanced by the coordination of urea with Br^- or Cl^-via hydrogen bonding. In contrast, the redox waves of the diruthenium complex become highly irreversible in the presence of relatively strong basic anions such as H₂PO₄^-, F^-, or OAc^-. This work demonstrates that the anion-urea interaction can be employed to regulate the electronic coupling and electron transfer between redox-active sites, suggesting the potential applications of the urea-functionalized diruthenium complex in anion sensing and stimuli-responsive molecular electronics.