Tuning the electronic communication and rates of intramolecular electron transfer of dimers of trinuclear ruthenium clusters: bridging and ancillary ligand effects.

Ten new bridged dimers of oxo-centered triruthenium clusters with CO and 4-(dimethylamino)pyridine (dmap), pyridine (py), or 4-cyanopyridine (cpy) as terminal ligands and pyrazine-d 4 (d 4 -pz), 2,5-dimethylpyrazine (dmpz), 2-methylpyrazine (mpz), and 2-chloropyrazine (clpz) as bridging ligands were prepared. The carbonyl stretching frequency, v(CO), was used as a probe for infrared spectroelectrochemical measurements. In the neutral and doubly reduced states, a single band was observed for each of the dimers, with a shift in frequency due to the oxidation state of the triruthenium clusters. In the singly reduced state, a range of v(CO) line shapes was observed, depending on the nature of the ligands, from two bands centered at the frequencies of the bands of the neutral and doubly reduced species to one broad band at the average of these two frequencies. By synthesizing new combinations of bridging and ancillary ligands, electronic communication between two bridged triruthenium clusters was effectively tuned, and electron-transfer rates were estimated by IR spectral line-shape analysis. In dimers bridged by the asymmetric ligand mpz, it was possible through selective isotope labeling of one CO ligand to observe "mixed-valence isomers," the two alternate charge distributions of a mixed-valence complex.