24162-09-2

Upstream product

• 66-71-7 1,10-Phenanthroline 
• 10049-08-8 ruthenium(III)chloride 
• 15878-95-2 tris(2,2'-bipyridyl)cobalt(II) 
• 41673-52-3 tris(1,10-phenanthroline)ruthenium(III)⁽³⁺⁾ 
• 69141-04-4 trichloro(2,2'-bipyridine)ruthenium 
• 59091-96-2 dichlorotetrakis(dimethylsulfoxide)ruthenium 

Downstream Products

• 63218-22-4 Co(1,3,6,8,10,13,16,19-octaazabicyclo[6.6.6]eicosane)⁽²⁺⁾ 
• 41673-52-3 tris(1,10-phenanthroline)ruthenium(III)⁽³⁺⁾ 
• 953507-12-5 [fac-(rhenium(I))Cl(CO)3(bathocuproinedisulfonate)]^(2-) 

Relevant academic research and scientific papers

Luminescent Ru(phen)n(bps)3-n2n-4 Complexes (n = 0-3) as Probes of Electrostatic and Hydrophobic Interactions with Micellar Media

The Ru(phen)n(bps)3-n2n-4 (n = 0-3) complexes (phen = 1,10-phenanthroline, bps = disulfonated 4,7-diphenyl-1,10-phenanthroline) were prepared to probe the hydrophobia and electrostatic interactions with cationic DTAB (n-dodecyltrimethylarnmonium bromide), anionic SDS (sodium dodecyl sulfate), and neutral C12E8 (n-dodecyl octaoxyethylene glycol monoether) surfactants. The measured emission maxima and lifetimes are consistent with the population of the Ru → phen MLCT (metal-to-ligand charge transfer) excited state in Ru(phen)32+ and the lower-lying Ru → bps MLCT excited state in Ru(phen)n(bps)3-n2n-4 (n = 0-2). Premicellar aggregates with oppositely charged surfactants lead to decreased overall emission intensity for all complexes. In particular, aggregates formed by Ru(bps)34- with DTAB exhibit a 22-fold decrease in emission intensity and marked changes in the electronic absorption spectrum, with a concomitant appearance of a shorter lifetime component. The photophysical characteristics of the premicellar adduct can be explained by changes in the relative energies of the emissive 3MLCT state and the 3ππ* state of the bps ligands, such that more effective deactivation of the 3MLCT through the 3ππ* state is possible. The results show that complexes possessing at least one bps ligand do not exhibit significant changes in their spectral properties upon addition of DTAB, C12E8, and SDS micelles, compared to those observed for Ru(phen)32+, interpreted as reduced interaction between bps-containing complexes and the micellized surfactants. The interactions (inferred from changes in spectral properties) between Ru(phen)32+ and the cationic DTAB system are greater than those of Ru(bps)2(phen)2- with the anionic SDS surfactant, although both complexes possess overall charge of equal magnitude. These observations can be explained in terms of the differences in the hydrophilicity of the complexes.

Bimolecular electron transfer in the Marcus inverted region

The rates for the photoinduced bimolecular reactions of a homologous series of Ru(II) diimines with cytochrome (cyt) c in its oxidized and reduced forms have been measured. The electronic coupling and reorganization energy of the system have been adjusted such that the inverted region may be accessed at reasonable driving forces. The electron transfer (ET) rate constants for *Ru(II) diimine/Fe(II)cyt c reaction increase monotonically and approach the diffusion limit of 8.8 x 108 M-1 s-1 at ΔG° = -0.7 V. At a higher driving force, which may be accessed with the powerfully oxidizing *Ru(diCF3-bpy)32+, the rate for ET is observed to drop off. Similarly, the high driving forces achieved with *Ru(II) diimine/Fe(III)cyt c (-ΔG ≤ 1.12 V) are manifested in a decrease of the ET rate constant with increasing exergonicity. The observed ET rates for both systems are well described by a bimolecular model for ET occurring over an equilibrium distribution of reactant separation distances, each having a different formation probability and weighted by the first-order ET rate constant. The unique observation of bimolecular ET in the inverted region is not due to a peculiar reaction pathway engendered by the Ru(II) diimines, which react as do other small-molecule cations at the solvent-exposed edge of the heme. The inherent ET properties of cyt c engender a Marcus curve that is displaced below the diffusion limit and shifted to smaller driving forces.

Dependence of spectroscopic, electrochemical, and excited-state properties of tris chelate ruthenium(II) complexes on ligand structure

Twelve tris chelate ruthenium(II) complexes, RuL32+, containing a series of structurally analogous diimine ligands (L) were prepared, and their spectroscopic, redox, and excited-state properties were studied in acetonitrile. Fairly good correlations between the reduction/oxidation potentials of RuL32+ and the reduction potential/pKa of L were obtained. Also, the metal-to-ligand charge-transfer (MLCT) absorption/emission energies were explicable in terms of the redox potentials of RuL32+. In contrast to the 2,2′-bipyridine (bpy) complex, three RuL32+ complexes, where L is 6-methyl-4-(2-pyridyl)pyrimidine, 6-phenyl-4-(2-pyridyl)pyrimidine, and 3,3′-bipyridazine, exhibited a small temperature dependence of the emission lifetime, indicating deactivation via thermal activation to the upper lying fourth MLCT excited state. RuL32+, where L is 2,2′-bipyrazine or 3,3′-bipyridazine, was superior to Ru(bpy)32+ in photosensitizing the photoreduction of methylviologen. Synthetic control of efficient photoredox sensitization is possible by modulating ligand properties: the π-accepting and σ-donating abilities of L.

Long Range Photoinduced Electron Transfer in a Rigid Polymer

Electron (hole) tunnelling reactions are studied in a rigid polymer medium by following the reductive quenching of a series of Ru(LL)3(2+)* homologues by a series of aromatic amines.Tunnelling distances up to 12 Angstroem (edge to edge) are observed.The e

Homogenous Catalysis of the Photoreduction of Water. 6. Mediation by Polypyridine Complexes of Rhuthenium(II) and Cobalt(II) in Alkaline Media

The emission of (polypyridine)rhutenium(II) complexes (S) is quenched by (polypyridine)cobalt(II) (CoL32+) complexes via parallel oxidative, reductive, and energy-transfer paths, giving CoL3 +S+, CoL33+ + S-, respectively.The oxidative route provides the basis for a new water photoreduction sequence: in mixed acetonitrile-water solvents relatively high cage-escape yields of Ru(4,7-(CH3)2phen)33+ and Co(bpy)3+(S = Ru(4,7-(CH3)2phen)32+, phen = 1,10-phenanthroline, bpy = 2,2'-bipyridine) are obtained.The Ru(III) complex is reduced by triethanolamine (TEOA), and the Co(bpy)3+ reacts with water and/or TEOAH+ to give H2. the maximum H2 quantum yield obtained is 0.29 in 50percent acetonitrile-water.Unusual features of the system are the fact that, at low TEOA, Co(bpy)32+ scavenging of Ru(III) reduces the H2 yield and that the cage-escape and limiting H2 yields are strongly solvent dependent: for the Ru(4,7-(CH3)2phen)32+-Co(bpy)32+-TEOA system the H2 yield increases from cca.0.02 in H2O to 0.29 in the mixed solvent.Reduction potentials for CoL33+/2+ and CoL32+/+ couples are also reported.