Abstract
A diruthenium complex with a free-base porphyrin linker 1 is synthesized and characterized by 1 H and 31 P NMR, IR, and ESI-TOF-MS spectroscopy. A cyclic voltammogram of 1 shows two reversible waves attributed to the redox processes at the ruthenium centers, and a compropotionation constant (K C ) has been determined to be 1.8 × 105, indicating that a mixed valence state of 1+ is thermodynamically stable. The monocationic complex 1+ obtained by chemical oxidation of 1 by [ Cp 2 Fe ] PF 6 shows an intervalence charge transfer (IVCT) band in the NIR region. On the basis of the electronic coupling ( V ab) of 2644 cm-1 obtained by analysis of the IVCT band, complex 1+• is assigned as a Class III compound according to the Robin–Day classification. DFT calculation and IR study suggest that the strength of π-back donation is one of key determinants for a strong electronic coupling between the two metal centers.
Published Version
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