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Photoinduced Electron Transfer in an Anthraquinone-[Ru(bpy)3]2+-Oligotriarylamine-[Ru(bpy)3]2+-Anthraquinone Pentad

A molecular pentad comprised of a central multielectron donor and two flanking photosensitizer-acceptor moieties was prepared in order to explore the possibility of accumulating two positive charges at the central donor, using visible light as an energy input. Photoinduced charge accumulation in purely molecular systems without sacrificial reagents is challenging, because of the multitude of energy-wasting reaction pathways that are accessible after excitation with two photons. As expected, the main photoproduct in our pentad is a simple electron-hole pair, and it is tricky to identify the desired two-electron oxidation product on top of the stronger signal resulting from one-electron oxidation.

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Reference£º
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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A catalyst don’t appear in the overall stoichiometry of the reaction it catalyzes, but it must appear in at least one of the elementary reactions in the mechanism for the catalyzed reaction. 37366-09-9, Name is Dichloro(benzene)ruthenium(II) dimer, molecular formula is C12H12Cl4Ru2. In a Article£¬once mentioned of 37366-09-9, category: ruthenium-catalysts

Locked and Loaded: Ruthenium(II)-Capped Cucurbit[ n]uril-Based Rotaxanes with Antimetastatic Properties

We report here the first coupling of Ru(II) units with cucurbit[6/7]uril-based pseudorotaxane ligands meant for biological application. The resulting ruthenium-capped rotaxanes were fully characterized, and a structure of one supramolecular system was determined by X-ray diffraction. Because the biological properties of Ru-based metallodrugs are tightly linked to the ligand-exchange processes, the effect of salt concentration on the hydrolysis of chlorides from the Ru(II) center was monitored by using 1H NMR spectroscopy. The biological activity of Ru(II)-based rotaxanes was evaluated for three selected mammalian breast cell lines, HBL-100, MCF-7, and MDA-MB-231. The antimetastatic activity of the assembled cationic Ru(II)-rotaxane systems, evaluated in migration assays against MCF-7 and MDA-MB-231 cell lines, is notably enhanced compared to that of RAPTA-C, a reference that was used. The indicated synergistic effect of combining Ru(II) with a pseudorotaxane unit opens a new direction in searching for anticancer supramolecular metallodrugs.

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Reference£º
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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Off-on-off fluorescence pH switch of three trinuclear RuII complexes containing imidazole rings

Three tripodal ligands H3L1-3 containing imidazole rings were synthesized by the reaction of 1,10-phenanthroline-5,6-dione with 1,3,5-tris[(3-formylphenoxy)methyl]benzene, 1,3,5-tris[(3-formylphenoxy)methyl]- 2,4,6-trimethylbenzene, and 2,2?,2?-tris[(3-formylphenoxy)ethyl] amine, respectively. Trinuclear RuII polypyridyl complexes [(bpy)6Ru3H3L1-3](PF 6)6 were prepared by the condensation of Ru(bpy) 2Cl2¡¤2H2O with ligands H 3L1-3. The pH effects on the UV/Vis absorption and fluorescence spectra of the three complexes were studied, and ground- and excited-state ionization constants of the three complexes were derived. The three complexes act as “off-on-off” fluorescence pH switch through protonation and deprotonation of imidazole ring with a maximum on-off ratio of 5 in buffer solution at room temperature.

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Reference£º
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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Structural properties of ruthenium biimidazole complexes determining the stability of their supramolecular aggregates

The results of a detailed investigation of the influence of substituents in a variety of ruthenium biimidazole-type complexes [Ru(R-bpy)2(R-bi(bz) imH2)]2+ (R = H, tBu; R = H, Me; bi(bz)imH2 = 2,2-bi(benz)imidazole) on selected structural and photophysical properties is reported. The photo-physical properties are only marginally influenced by the substituents at the bipyridine and the bi-imidazole core. All complexes show intense absorptions in the visible range of the spectrum with maxima around 475 nm, and emission from the formed excited state occurs at wavelengths between 650 and 670 nm. The comparison of structural properties determined by X-ray analysis within a series of related complexes shows that the Ru-N bond lengths to the coordinated bipyridines are not significantly influenced by the substituents, but slight differences in the Ru-N bond lengths to the biimidazole-type ligands can be detected. The reactions between ruthenium complexes containing different biimidazole-type ligands with the sulfate dianion, however, show a strong correlation between the substituents at the biimidazole core and the solubility of the product. The bibenzimidazole-containing complexes precipitate from aqueous solution whereas the ruthenium complex containing unsubstituted biimidazole stays in solution. The solid-state structure of one example of the sulfate-containing products (2b) shows that strong hydrogen bonds between the secondary amine function of the bibenzimidazole and the oxygen functionalities of the sulfate contribute to this unexpected behavior.

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Reference£º
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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Reference of 37366-09-9. Let¡¯s face it, organic chemistry can seem difficult to learn. Especially from a beginner¡¯s point of view. Like 37366-09-9, Name is Dichloro(benzene)ruthenium(II) dimer. In a document type is Article, introducing its new discovery.

Synthesis, characterization and interactions with 9-methylguanine of ruthenium(II) eta6-arene complexes with aromatic diimines

The complexes of the formula [(eta6-arene)Ru(L)Cl]PF6, where arene is benzene (bz) or p-cymene (cym) and L is 2,(2?-pyridyl)quinoline (pqn), were synthesized and characterized by means of NMR spectroscopic techniques, HR-ESI mass spectrometry and, in the case of [(eta6-cym)Ru(pqn)Cl]PF6, by X-ray single crystal diffraction. Their resistance in hydrolysis was also studied. A comparative NMR study of their 9-methylguanine (9-MeG) complexes, [(eta6-arene)Ru(pqn)(9-MeG)](PF6)2, with similar diimine complexes revealed that the unimpeded rotation of 9-MeG is hindered by interactions between the 9-MeGO6 and the p-cymene aromatic proton H2 and, by the bulky shape of the pqn. This conformation forces the 9-MeGH8 to be in close proximity to the aromatic ring system of pqn. NMR spectroscopic techniques lead to the conclusion that the strong shielding effect on 9-MeGH8 depends on the extension of the aromatic system of the ligand. Also, we conclude that the strong deshielding on the 9-MeGNH1 is influenced by both the N7 ruthenation of 9-MeG and the addendum electron density in the 9-MeG ring system, due to the proximity to the aromatic ring system of pqn.

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Reference£º
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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Luminescent ruthenium(II) bipyridyl-phosphonic acid complexes: pH dependent photophysical behavior and quenching with divalent metal ions

The synthesis, redox behavior, and photophysical properties of a series of Ru(II) bipyridyl complexes having diimine ligands with phosphonate and phosphonic acid substituents are presented. The phosphonate-containing ligands examined include diethyl 4-(2,2′-bipyrid-4-yl)benzylphosphonate (bpbzp), diethyl 4-(2,2′-bipyrid-4-yl)phenylphosphonate (bppp), and 4,4′-(diethyl phosphonato)-2,2′-bipyridine (bpdp), and the [(bpy)2Ru(L)](PF6)2 complexes of both the diethyl phosphonate and the phosphonic acid were prepared. The Ru(III/II) potentials are more positive for the phosphonate complexes than for the phosphonic acids, and the first reduction is localized on the phosphonate-containing ligand for the bppp and bpdp complexes. The first reduction of the phosphonic acid complexes is at more negative potentials and cannot be distinguished from bpy reduction. For the bppp and bpdp complexes luminescence arises from a Ru(dpi) ? bpy-phosphonate (pi*) MLCT state; the phosphonic acid complexes luminesce at higher energies from a MLCT state not clearly isolated on one ligand. Iron(III) and copper(II) complex with and very efficiently quench the luminescence of all the phosphonic acid complexes in nonaqueous solvents. The quenching mechanism is discussed on the basis of luminescence decay and picosecond transient absorption measurements.

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Reference£º
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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Strategies for optimizing the performance of cyclometalated ruthenium sensitizers for dye-sensitized solar cells

Pursuant to our goal of optimizing the performance of cyclometalated Ru sensitizers in the dye-sensitized solar cell (DSSC), the physicochemical properties of a series of tris-heteroleptic RuII complexes are reported. Each of these complexes contains a metal ligated by: (i) a bidentate 2,2?-bipyridine-4,4?-dicarboxylic acid (dcbpy) ligand to anchor the dye to the TiO2 surface; (ii) a cyclometalating ligand – withelectron-withdrawing groups to ensure a sufficiently high oxidation potential for dye regeneration in the DSSC; and (iii) a 2,2?-bipyridine (bpy) ligand. UV/Vis and electrochemical data reveal that each complex exhibits broad metal-to-ligand charge transfer (MLCT) bands of significant intensity (Imu = 1.0-2.3 A – 104 M-1 cm-1) in the visible region, and ground- and excited-state redox potentials that are appropriate for sensitizing TiO2. Analysis of the dyes in the DSSC highlights the sensitivity of cell performance to the oxidation potential for each of the dyes, which has important implications in the development of cyclometalated Ru sensitizers.

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Reference£º
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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37366-09-9, Name is Dichloro(benzene)ruthenium(II) dimer, molecular formula is C12H12Cl4Ru2, belongs to ruthenium-catalysts compound, is a common compound. In a patnet, once mentioned the new application about 37366-09-9, Computed Properties of C12H12Cl4Ru2

[Ru(phgly)2(binap)]/Li2CO3: A Highly Active, Robust, and Enantioselective Catalyst for the Cyanosilylation of Aldehydes

The right combination: A series of aromatic, heteroaromatic, aliphatic, and alpha,beta-unsaturated aldehydes can be converted into the desired silylated cyanohydrins by reaction with (CH3)3SiCN and a catalyst system consisting of the combination of a chiral ruthenium complex and Li2CO3 (see scheme). The reaction is highly enantioselective and affords the R products with up to 98% ee within 24 h at a substrate-tocatalyst ratio of 10000:1. (Chemical Equation Presented).

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Reference£º
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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Synthesis, characterization, and photochemical behavior of {Ru(arene)} 2+ derivatives of alpha-[PW11O39] 7-: An organometallic way to ruthenium-substituted heteropolytungstates

Reaction of [Ru(arene)Cl2]2 (arene = benzene, toluene, p-cymene, hexamethylbenzene) with K7[PW11O 39]¡¤14H2O provided two series of organometallic derivatives of heteropolytungstates: type-1 and type-2 complexes of general formulas [PW11O39{Ru(arene)(H2O)}]5- and [{PW11O39{Ru(arene)}}2{WO 2}]8-, respectively. All compounds were characterized by infrared and multinuclear NMR (1H, 31P, 183W) spectroscopies. The crystal structures of Na4K4-[{PW 11O39{Ru(benzene)}}2{WO2}] ¡¤6H2O (NaK-2a¡¤6H2O), K7H[{PW 11O39{Ru(toluene)}}2{WO2}] ¡¤4H2O (K-2b¡¤4H2O), and Cs3K 2[PW11O39{Ru(p-cymene)(H2O)}] ¡¤4H2O (CsK-1c-4H2O) were obtained and revealed that the {Ru(arene)} fragment is supported on the oxometallic framework. Photochemical reactivity of [PW11O39{Ru(arene)(H 2O)}]5- (arene = toluene, p-cymene) in the presence of various ligands L (L = H2O, dimethyl sulfoxide, tetramethylene sulfoxide, and diphenyl sulfoxide) was investigated, and led to the formation of [PW11O39{Ru(L)}]5-, in which the ruthenium is incorporated into the lacunary [PW11O39]7- anion.

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Reference£º
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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Kinetics and Mechanism of the Stereochemical Isomerization of an Arene-Ruthenium Complex of the Atropisomeric Ligand 1,1?-Biphenyl-2,2?-diamine

(eta 6-Benzene)(delta/lambda-1,1?-biphenyl-2,2?-diamine) chlorometal(II) hexafluorophosphate (1; metal = ruthenium, osmium) have been synthesized. The rigid nature of the seven-membered chelate ring formed by the 1,1?-biphenyl-2,2?-diamine (dabp) ligand renders the complexes chiral. The resulting C1 molecular symmetry of 1(M=Ru) that we have observed in the solid state by single-crystal X-ray crystallography is preserved in solution on the NMR time scale. The four N-H protons of 1(M=Ru,Os) are chemically inequivalent in the 1H NMR spectrum at 20C. Spin-perturbation NMR experiments in acetone solutions reveal pairwise exchange of the resonances that correspond to the N-H protons on the spin-relaxation time scale. The three mechanisms that would account for such an exchange (atropisomerization of the dabp ligand, inversion of stereochemistry at the metal center, and simultaneous inversion of the stereochemistry at the metal and the ligand) are distinguishable, provided a proper assignment of the four N-H protons can be made in the NMR spectra. Having made that assignment, we conclude from 2D EXSY NMR spectroscopy that the mechanism of exchange is inversion of stereochemistry at the dabp ligand center. This observation contrasts with previous reports that conformational isomers of dabp can be resolved.

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Reference£º
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI