Photosubstitution reactions of Ru(bpy)2XYn+ complexes

Photo-Induced Pyridine Substitution in cis-[Ru(bpy)2(py)2]Cl2: A Snapshot by Time-Resolved X-ray Solution Scattering

“…Conversely, more is known on the femtosecond timescale of the photorelease of ligands such as CO. 33,64 On the basis of this first exciting result, future applications of TR-WAXS to photoactivatable metal anticancer agents can now be envisaged, including study of their photochemistry on shorter time-scales (1-100 ns), in biological conditions (e.g., salts, peptides, metabolites), and in the presence of target macromolecules relevant to tumor cells.…”

Ruthenium polypyridyl phototriggers: from beginnings to perspectives

“…Direct excitation from the ground state is forbidden, and the corresponding absorption band cannot be detected in the UV-visible spectrum of the complex. It is the highly absorptive MLCT band, the one responsible for the capture of the photons, that will be funnelled to the d-d state [5].…”

“…The photochemical mechanism of Ru-bpy imposes some restrictions regarding the energy of the photons capable of eliciting the ligand release [5]. The energy-quantum yield relationship implies that it is difficult-if not impossible-to design a phototrigger with both high absorption at long wavelengths and high photodissociation quantum yield.…”

“…[Ru(bpy) 2 XY] n+ , share some of the photophysics of [Ru(bpy) 3 ] 2+ complexes, but their photochemistry is dominated by the photodissociation of one or both of the monodentate ligands, in a well-defined pathway. Although the photoreactivity of [Ru(bpy) 2 XY] n+ was reported by Dwyer et al [4], the first systematic study on the photochemistry of these compounds was performed by Pinnick & Durham [5] two decades later. They measured the quantum yield of photosubstitution of several complexes, showing that it correlates with the absorption maxima of the bands involved and with the redox potential (E 1/2 ) of the Ru(II)/Ru(III) couple.…”

Propriedades fotoquímicas e fotofísicas, e investigação teórica de um novo monômero-complexo de Ru(II)-bipiridina

“…Nesse sentido, a substituição da bpy pelo 3amdpy 2 A ocorrência da reação de perda da 3amnpy é esperada como já observado em reações similares para complexos semelhantes de Ru (cis-[Ru(bpy) 2 L 2 )], L = piridina e piridinas substituídas) [100]. Para esses complexos, a eficiência da fotorreação é dependente do substituinte da piridina e da diferença de energia entre os estados MC e MLCT.…”