Effect of electronic structure on the photoinduced ligand exchange of Ru(II) polypyridine complexes.

The series of complexes [Ru(bpy)(2)(L)](2+), where bpy = 2,2'-bipyridine and L = 3,6-dithiaoctane (bete, 1), 1,2-bis(phenylthio)ethane (bpte, 2), ethylenediamine (en, 3), and 1,2-dianilinoethane (dae, 4), were synthesized, and their photochemistry was investigated. Photolysis experiments show that the bisthioether ligands in 1 and 2 are more easily photosubstituted by chloride ions, bpy, and H(2)O than the corresponding diammine complexes in 3 and 4 to generate the bis-substituted products. Electronic structure calculations show that bond elongation in the lowest energy triplet metal-to-ligand charge transfer ((3)MLCT) state compared to the ground state is greater for complexes containing bisthioether ligands than those with coordinated bidentate nitrogen atoms. This elongation in the excited state is attributed to Ru-S π-bonding character of the highest occupied molecular orbitals, which is not present in the diamine complexes. In the Ru→bpy (3)MLCT state, the lower electron density on the metal-centered highest occupied molecular orbital (HOMO) weakens the Ru-S bond and results in the greater photoreactivity of 1 and 2 relative to that of 3 and 4. The more efficient photoinduced ligand exchange of the complexes possessing thioether ligands results in binding of 1 and 2 to DNA upon irradiation.