Inter- or intramolecular electron transfer between triruthenium clusters: we’ll cross that bridge when we come to it

The purpose of this review is to examine the fundamental differences between intermolecular self-exchange vs. intramolecular ET in mixed-valence complexes based on similar triruthenium structural units. The role of orbital overlap between ancillary ligands of the electron donor and acceptor are considered in self-exchange reactions which are found to be strongly adiabatic and again in bridged mixed-valence systems. The method of infrared (IR) reflectance spectroelectrochemistry for the determination of extremely fast (1011–1013 s−1) ET rate constants is reviewed as a tool to provide quantitative information about the time scales of localization and delocalization. The role of internal vibrations of the bridging ligand in strongly delocalized mixed-valence ions is investigated by resonance Raman and IR spectroscopies. The role of solvent dipolar relaxation times in determining the rates of ultrafast intramolecular ET reactions is reviewed in the context of inorganic mixed-valence chemistry. Finally, the concept of Robin–Day Class II/III “borderline” complexes is considered, and a concise definition of the localized to delocalized transition is provided in terms of the relative contributions of external solvent and internal complex ion vibrational modes to ET.