jp4085684_si_001.pdf (1.52 MB)
Download fileSelective Photoinduced Ligand Exchange in a New Tris–Heteroleptic Ru(II) Complex
journal contribution
posted on 2013-12-19, 00:00 authored by Bryan
A. Albani, Christopher B. Durr, Claudia TurroThe
complex cis-[Ru(biq)(phen)(CH3CN)2]2+ (1, biq = 2,2′-biquinoline,
phen = 1,10-phenathroline) displays selective photosubstitution of
only one CH3CN ligand with a solvent molecule upon irradiation
with low energy light (λirr ≥ 550 nm), whereas
both ligands exchange with λirr ≥ 420 nm.
In contrast, [Ru(phen)2(CH3CN)2]2+ (2) and [Ru(biq)2(CH3CN)2]2+ (3) exchange both CH3CN ligands
with similar rates upon irradiation with a broad range of wavelengths.
The photolysis of 1 in the presence of pyridine (py)
results in the formation of the intermediate cis-[Ru(biq)(phen)(py)(MeCN)]2+, which was isolated and characterized by X-ray crystallography,
revealing that the CH3CN positioned trans to the phen ligand is more photolabile than that positioned trans to the biq ligand when irradiated with low energy
light. These results are explained using the calculated stabilities
of the two possible products, together with the molecular orbitals
involved in the lowest energy excited state.
