Conformational Tuning of the Intramolecular Electronic Coupling in Molecular‐Wire Biruthenium Complexes Bridged by Biphenyl Derivatives

The synthesis and characterization of a series of biphenyl‐derived binuclear ruthenium complexes with terminal {RuCl(CO)(PMe₃)₃} moieties and different structural arrangements of the phenyl rings are reported. Electrochemical studies revealed that the two metal centers of the binuclear ruthenium complexes interact with each other through the biphenyl bridge, and the redox splittings ΔE_1/2 show a strong linear correlation with cos² ?, where ? is the torsion angle between the two phenyl rings. A combination of electrochemical, UV/Vis/NIR, and in situ IR differential spectroelectrochemical analysis clearly showed that: 1) the intramolecular electronic couplings in the binuclear ruthenium complexes could be modulated by changing ?; 2) the electronic ground state of the mixed‐valent cations changes from delocalized to localized through the biphenyl bridge with increasing torsion angle ?, that is, the redox processes of these complexes change from significant involvement of the bridging ligand to an oxidation behavior with less participation of the bridge.