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Synthesis, characterization and electronic properties of trans-[4-(alkoxycarbonyl)phenyl]porphyrin-[RuII(bpy) 3]2 complexes or boron-dipyrrin conjugates as panchromatic sensitizers for DSSCs

Two porphyrin-based dyes were synthesized that incorporate two additional chromophores to absorb in a wider UV/Vis region. In the first dye, a porphyrin ring is linked through an amide bond to two [Ru(bpy)3]2+ units, forming a symmetric [Ru(bpy)3]-porphyrin-[Ru(bpy)3] {Por(COOH)2[Ru(bpy)3]2} system. The second porphyrin is trans substituted through a triple bond to the meso position with two boron dipyrrin (BDP) molecules {Por(COOH)2(BDP)2}. Both porphyrins bear two carboxylic groups capable of binding onto a TiO 2 surface, with potential applications in dye-sensitized solar cells (DSSCs). The title dyes were characterized by means of 1H and 13C NMR spectroscopy, elemental analysis, MALDI-TOF, UV/Vis absorption and emission studies. Copyright

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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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Rapid water oxidation electrocatalysis by a ruthenium complex of the tripodal ligand tris(2-pyridyl)phosphine oxide

The tris(2-pyridyl)phosphine oxide (Py3PO) complex [Ru(Py3PO)(bpy)(OH2)]2+ (bpy is 2,2?-bipyridine) is a pH-dependent water oxidation electrocatalyst that accelerates dramatically with increasing pH – up to 780 s-1 at pH 10 (?1 V overpotential). Despite retaining the pentakis(pyridine) ligand arrangement common to previously reported catalysts, the tripodal Py3PO ligand framework supports much faster electrocatalysis. The early stages of the catalytic cycle are proposed to follow the typical pattern of single-site ruthenium catalysts, with two sequential 1H+/1e- proton-coupled electron transfer (PCET) oxidations, but the pH-dependent onset of catalysis and rapid rates are distinguishing features of the present system. This journal is

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

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Ligand-Tuned C?H Bond Activation/Arylation of 2-Arylpyridines over Pyridine-Based N,O/N,N Ligated Ruthenium?Arene Complexes

Water-soluble ruthenium(II)?arene complexes [(eta6-arene)Ru(kappa2-L)]n+ (n = 0, 1) ([Ru]-1?[Ru]-10) containing pyridine-based bischelating N,O/N,N donor ligands (L1?L5) are synthesized and employed for the catalytic C?H bond activation/arylation of a wide range of 2-phenylpyridines and aryl halides in water, affording the corresponding mono- and biarylated products. Exploring the reactivity of the synthesized complexes, our investigations, including time-dependent 1H NMR spectroscopic studies with ruthenium?arene catalysts, demonstrate a remarkable structure?activity relationship for the ligand-tuned C?H activation/arylation of 2-phenylpyridine, where the complexes with bischelating N,O donor-based ligands (acteylpyridine and picolinate) outperform those with N,N donor ligands (iminopyridine). Moreover, among the N,O donor ligands, a distinct effect of the nature of the coordinating oxygen donor on the catalytic activity is also observed, where ruthenium?arene complexes having N,O donor ligands (acetylpyridine) with neutral oxygen-donor atoms exhibit enhanced catalytic activity over those with anionic oxygen-donor atoms (picolinate). The observed trend in the catalytic activity is attributed to the ligand-promoted facile deprotonation and coordination?decoordination interconversion behavior. In addition, molecular structures for a few of the representative complexes ([Ru]-2, [Ru]-4, and [Ru]-5) are authenticated by single-crystal X-ray diffraction studies.

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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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New Ru(II) chromophores with extended excited-state lifetimes

We describe the synthesis, electrochemical, and photophysical properties of two new luminescent Ru(II) diimine complexes covalently attached to one and three 4-piperidinyl-1,8-naphthalimide (PNI) chromophores, [Ru(bpy)2(PNI-phen)](PF6)2and [Ru(PNI-phen)3](PF6)2 respectively. These compounds represent a new class of visible light-harvesting Ru(II) chromophores that exhibit greatly enhanced room-temperature metal-to-ligand charge transfer (MLCT) emission lifetimes as a result of intervening intraligand triplet states (3IL) present on the pendant naphthalimide chromophore(s). In both Ru(II) complexes, the intense singlet fluorescence of the pendant PNI chromophore(s) is nearly quantitatively quenched and was found to sensitize the MLCT-based photoluminescence. Excitation into either the 1IL or 1MLCT absorption bands results in the formation of both 3MLCT and 3IL excited states, conveniently monitored by transient absorption and fluorescence spectroscopy. The relative energy ordering of these triplet states was determined using time-resolved emission spectra at 77 K in an EtOH/MeOH glass where dual emission from both Ru(II) complexes was observed. Here, the shorter-lived higher energy emission has a spectral profile consistent with that typically observed from 3MLCT excited states, whereas the millisecond lifetime lower energy band was attributed to 3IL phosphorescence of the PNI chromophore. At room temperature the data are consistent with an excited-state equilibrium between the higher energy 3MLCT states and the lower energy 3PNI states. Both complexes display MLCT-based emission with room-temperature lifetimes that range from 16 to 115 mus depending upon solvent and the number of PNI chromophores present. At 77 it is apparent that the two triplet states are no longer in thermal equilibrium and independently decay to the ground state.

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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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Transfer hydrogenation of ketones catalysed by new half-sandwich ruthenium(II) complexes bearing the sulfonated phosphane (meta-sulfonatophenyl) diphenylphosphane potassium salt (TPPMS)

New half-sandwich ruthenium(II) complexes [RuCl2(eta 6-arene)(TPPMS)] [eta6-arene = p-cymene (1a), benzene (1b)] and [RuCl(eta6-arene)(TPPMS)2][Cl] [eta6-arene = p-cymene (2a), benzene (2b)] containing the water-soluble (meta-sulfonatophenyl)diphenylphosphane potassium salt (TPPMS) have been synthesised. The X-ray analysis for complex 1a revealed that, in the solid state, complex anions are held together in the crystal lattice by weak electrostatic interactions with potassium cations leading to a linear chain structure. The extent of the association in solution depends on the solvent and the determination of the size of the particles in THF can be accomplished using Multiangle Light Scattering (MALS). The new complexes proved to be excellent catalysts for transfer hydrogenation of ketones and the hydrophilic properties of the TPPMS ligand allow the catalyst recovery. The hydride derivative [RuClH(eta6-p-cymene)(TPPMS)] (4) has also been shown to be an efficient catalyst for these processes. Moreover, when 1a was used as catalyst, complex 4 was observed as the main product after the catalysis, supporting the implication of hydride species in transfer hydrogenation catalysis. Wiley-VCH Verlag GmbH & Co. KGaA, 2006.

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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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15746-57-3, Name is Cis-Dichlorobis(2,2′-bipyridine)ruthenium(II), molecular formula is C20H16Cl2N4Ru, belongs to ruthenium-catalysts compound, is a common compound. In a patnet, once mentioned the new application about 15746-57-3, Computed Properties of C20H16Cl2N4Ru

Structure, spectroscopy and electrochemistry of the bis(2,2?-bipyridine)(salicylato)ruthenium(II) complex

The bis(2,2?-bipyridine)(salicylato)ruthenium(II) complex has been prepared and characterized by means of single crystal X-ray diffraction, electrochemistry and resonance Raman spectroscopy. The electronic bands in the visible region have been assigned to Ru-bipy charge-transfer transitions and discussed in terms of ZINDO/S semiempirical calculations. Spectroelectrochemical measurements have been performed in order to elucidate the nature of the electrochemical waves in the cyclic voltammograms. The green complex generated by oxidation of the complex at 0.25 V has been isolated, revealing substantial ruthenium-salicylate electronic mixing, as deduced from the corresponding resonance Raman spectra. Further oxidations at 1.2 and 1.4 V have been observed and ascribed to hydroxylation of the salicylate semiquinone ligand in the complex.

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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 of the Ruthenium Imido Complexes, 2 (R = Pri or Me), and the Crystal Structure of 2

Rhutenium imido complexes, <(eta-C6H6)Ru(N-2,6-R2C6H3)>2 (R = Pri 1, Me2), have been synthesised by the room temperature reaction of <(nu-C6H6)-RuCl2>2 with 2 equiv. of LiNH(2,6-R2C6H3) and 1 has been shown by single-crystal X-ray diffraction to be a symmetrical, imido-bridged dimer containing a bent Ru2N2 bridge.

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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 and characterization of two novel, mono-lacunary Dawson polyoxometalate-based, water-soluble organometallic ruthenium(II) complexes: Molecular structure of [{(C6H6)Ru(H2O)} (alpha2-P2W17O61)]8-

The synthesis and structural characterization of a novel class of mono-lacunary Dawson polyoxometalate-(POM-)based, water-soluble organometallic complexes, which are expected to be effective homogeneous oxidation catalyst precursors in water, is described. The organometallic complexes K 8[{(C6H6)Ru(H2O)} (alpha2-P2W17O61)]¡¤12H 2O (1) and K8[{(p-cymene)Ru(H2O)} (alpha2-P2W17O61)]¡¤16H 2O (2) were successfully prepared by direct reactions of the mono-lacunary Dawson POM K10[alpha2-P2W 17O61]¡¤19H2O with the organometallic precursors [(C6H6)RuCl2]2 and [(p-cymene)RuCl2]2, respectively, in aqueous media and characterized by complete elemental analysis, thermogravimetric and differential thermal analyses (TG/DTA), and FT-IR and solution (1H, 13C, 31P, and 183W) NMR spectroscopy. The molecular structure of [{(C6H6)Ru(H2O)} (alpha2-P2W17O61)]8- (1a), in which the binding of the cationic organometallic group {(C 6H6)Ru(H2O)}2+ occurs through two oxygen atoms of the four available oxygen atoms in the mono-lacunary site of the POM, resulting in overall C1 symmetry, was successfully determined by single-crystal X-ray analysis. Interestingly, the hydrophilicity of the organometallic precursors is greatly enhanced by binding to a mono-lacunary Dawson POM with higher hydrophilicity. Wiley-VCH Verlag GmbH & Co. KGaA, 2006.

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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, photophysical, and electrochemical properties of two novel trinuclear Ru(II) polypyridyl complexes

Two polypyridyl ligands 2,2?,2?-tris((4,5-diazafluoren-9-yliminoxy)ethyl)amine (L1) and 1,3,5-tris((4,5-diazafluoren-9-yliminoxy)methyl))-2,4,6-trimethylbenzene (L2), and corresponding trinuclear Ru(II) complexes [(bpy)6L1-2(RuII)3](PF6)6 (Ru-L1, Ru-L2) have been synthesized. Cyclic voltammetry of the complexes are consistent with one Ru(II)-centered oxidation at 1.32 V and four ligand-centered reductions. Photophysical behaviors are investigated by UV-Vis absorption and fluorescence spectrometry. The two complexes show metal-to-ligand charge transfer absorption at 440 nm and emission at around 580 nm.

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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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Syntheses, structures, and catalytic properties of two arene-ruthenium(II) complexes bearing N-(2-pyridinyl)aminodiphenylphosphine sulfide ligands

Treatment of [(arene)Ru(mu-Cl)Cl]2 with Ph2P(S)NH(2-py) in the presence or absence of base gave two arene-ruthenium(II) complexes [(eta6-p-cymene)Ru{kappa2-N,N-Ph2P(S)N(2-py)}Cl] (1) and [(eta6-benzene)Ru{kappa1-N-Ph2P(S)NH(2-py)}Cl2] (2), which have been characterized by infrared, nuclear magnetic resonance spectroscopies, and mass spectrometry along with microanalyses. Crystal structures of Ph2P(S)NH(2-py) ¡¤ 1/4C6H14, 1 and 2 ¡¤ 1/2CH2Cl2 were determined by single-crystal X-ray diffraction. Two arene-ruthenium(II) complexes were tested as precatalysts for the transfer hydrogenation of acetophenone to give 1-phenyl ethanol.

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