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The synthesis of a new, robust fluorescence-resonance-energy-transfer (FRET) system is described. Its donor chromophore is derived from an N-allyl-substituted quinolinone attached to 4-bromophenyl-alanine via Heck cross-coupling. The resulting Fmoc-protected derivative 11 was used as building block in solid-phase peptide synthesis (SPPS). As FRET acceptor, a sulfonylated ruthenium(II)-bathophenanthroline complex with a peripheral COOH function was prepared for covalent attachment to target molecules. The UV/VIS absorption and emission spectra of peptides bearing only the donor (D) or acceptor (A) dye showed a good overlap of the emission band of the donor with the absorption band of the acceptor. The fluorescence spectra of a peptide bearing both dyes revealed an additional emission after excitation of the donor, which is due to indirect excitation of the acceptor via FRET. The long fluorescence lifetime of the RuII complex (0.53 mus) makes it well-suited for time-resolved measurements. As a first application of this new FRET system, the peptide 18, with the recognition sequence for the protease thrombin, flanked by the two dyes, was synthesized and successfully cleaved by the enzyme. The change in the ratio of the fluorescence intensities could be determined.

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

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Three ruthenium(II) complexes with N-heterocyclic carbene (NHC) or NHC/2,2?:6?,2?-terpyridine (tpy) hybrid ligands, bis[2,6-bis(3-methylimidazol-3-ium-1-yl)pyridine-4-carboxylic acid]ruthenium(II) (BCN), [2,6-bis(3-methylimidazolium-1-yl)pyridine-4-carboxylic acid](2,2?;6?2?-terpyridine)ruthenium(II) (TCN), and [2,6-bis(3-methylimidazol-3-ium-1-yl)pyridine](2,2?;6?2?- terpyridine-4?-carboxylic acid)ruthenium(II) (CTN), have been synthesized and characterized by 1H and 13C NMR, high-resolution mass spectrometry, and elemental analysis. The molecular geometry of the TCN complex was determined by X-ray crystallography. Electronic absorption spectra of these complexes exhibit typical pi-pi* and metal-to-ligand charge transfer bands in the UV and visible regions, respectively. The lowest energy absorption maxima were 430, 448, and 463 nm with molar extinction coefficients of 28 100, 15 400, and 7400 M-1cm-1 for BCN, TCN, and CTN, respectively. Voltammetric data suggest that energy levels of the highest occupied molecular orbitals (HOMOs) of the three complexes reside within a 10 meV window despite the varying degrees of electronic effect of the constituent ligands. The electronic structures of these complexes calculated via density functional theory (DFT) indicate that the three HOMOs and the three lowest unoccupied MOs (LUMOs) are metal and ligand centered in character, for the former and the latter, respectively. Time-dependent DFT (TD-DFT) calculation predicts that the lowest energy absorption bands of each complex are comprised of multiple one-electron excitations. TD-DFT calculation also suggests that the background of spectral red shift stems most likely from the stabilization of unoccupied MOs rather than the destabilization of occupied MOs. The overall efficiencies of the dye-sensitized solar cell systems of these complexes were found to be 0.48, 0.14, and 0.10% for BCN, TCN, and CTN, respectively, while that of a commercial bis(4,4?-dicarboxylato-2,2?-bipyridine)- bis(isothiocyanoto)ruthenium(II) (N719) system was 6.34%.

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

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Combined electrochemical and dilatometry measurements were used to characterize the transport of hydrogen through thin RuO2 layers coated on palladium wire electrodes. Hydrogen dissolved in aqueous solutions penetrated through the oxide in a pH-dependent mechanism that combined diffusion of molecular hydrogen and pH-dependent proton hopping through redox sites within the oxide lattice. When cathodically charged, hydrogen was generated and absorbed at the oxide-solution interface only after Ru (IV) reduction occurs, and then, transported into the metal.

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

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In this work, a-CNx films prepared by DC magnetron sputtering on stainless steel substrate have been investigated as electrode materials. While their wide potential window was confirmed as a property shared by boron doped diamond (BDD) electrodes, their electrochemical activity with respect to fast and reversible redox systems, [Ru(NH3)6]3+/2+, [Fe(CN) 6]3-/4- and [IrCl6]2-/3-, was assessed by Electrochemical Impedance Spectroscopy (EIS) after cathodic or anodic electrochemical pre-treatments or for as grown samples. It was shown for the three systems that electrochemical reactivity of the a-CNx films was improved after the cathodic pre-treatment and degraded after the anodic one, the apparent heterogeneous rate constant k0app being decreased by at least one order of magnitude for the latter case. A high k0app value of 0.11 cm s-1 for [IrCl6]2-/3- was obtained, close to the highest values found for BDD electrodes.

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

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Novel heterogeneous photocatalysts were developed which are able to transfer electrons from excited Ru(II) donors within the zeolite framework to Co(III) acceptor complexes in the exterior. The materials were prepared and characterized by elemental analysis, electrochemical methods, diffuse reflectance, and raster and transmission electron microscopy. The catalysts consist of zeolite Y-encapsulated Ru(bpy)32+ (bpy = 2,2a¿²-bipyridine) sensitizers in close proximity to TiO2 nanoparticles on the same support. The photophysical properties of Ru(bpy)32+ within the zeolite supercages were investigated at different loadings of Ru(bpy)32+ and TiO2. The photoexcited MLCT state of the zeolite-entrapped Ru(bpy)32+ reacts via electron transfer with Co(dpphen)33+ (dpphen = 4,7-diphenyl-1,10-phenanthroline) in the exterior of the zeolite particles. The relative quenching of Ru(bpy)32+ by external Co(dpphen)33+ increases as the TiO2 content within the zeolite is increased, where electron transfer from Ru(bpy)32+ complexes within the interior of the zeolite are able to transfer electrons to Co(dpphen)33+. This observation indicates that electrons can be transported from the interior of the zeolite to the surface in the presence of an appropriate electron relay, such as TiO2 nanoparticles.

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

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Nitrosyl chloride reacts with hydrated ruthenium trichloride in the presence of triphenylphosphine (Ru : PPh3 = 1:8) to give the pink RuIII high spin complex NH4, NH4Cl, and the green 7 d electron complex 2 which reacts with PPh3 to give the yellow 7 d electron complex Ru(NO)Cl2(PPh3)2.

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

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A fast and efficient phenylselenylation of allyl acetates by diphenyl diselenide and indium(i) bromide has been achieved in neat under the catalysis of Ru(acac)3. The intermediate complex of diphenyl diselenide and indium has been isolated and identified as a polymeric pentacoordinated In(iii) selenolate complex, [In(SePh)3]n.

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

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Hydrogenation of arene derivatives can be successfully performed in water by using ruthenium(0) nanoparticles stabilized by 1: 1 inclusion complexes formed between methylated cyclodextrins and an ammonium salt bearing a long alkyl chain. The Royal Society of Chemistry.

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

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The purpose of this investigation is to synthesize formic acid by hydrogenation of CO2. The catalysts or catalyst precursors employed in these studies under 6 MPa(CO2/H2) and at 60C, were ruthenium chloride or ruthenium complexes. The turnover number obtained for formic acid production was ca. 200 by using ethanol/water (5:1) for a 5 h reaction period. In the reaction mechanism the CO2 is activated by the ruthenium complex with formation of metal-formate intermediate HCO2RuH(CO)(PPh3)3, which releases formic acid by reductive elimination of the hydrido-formate ligands.

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

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Single-crystal X-ray studies on beta-RuCl3 and RuBr 3 at different temperatures verified, that both compounds are dimorphic and show reversible phase transitions at 206 K resp. 384 K. In the HT-forms the Aristo-type of the hexagonal TiI3-structure with space group P63/m c m (Z = 2, beta-RuCl3 at 293(2) K: a = 6.121(2) A, c =5.655(2) A, RuBr3 at 423(3) K: 6.5215(12) A, c = 5.8851(13) A) has been found, in the LT-forms the RuBr 3-type structure, an orthorhombic distorted variant with space group Pmmn (Z = 4, beta-RuCl3 at 170(3) K: a = 10.576(2) A, b = 5.634(1) A, c = 6.106(1) A, RuBr3 at 293(2) K: a =11.2561(16) A, b = 5.8725(12) A, c = 6.4987(9) A). A hexagonal closest packing of X- anions forms the basis of an arrangement of infinite chains with face-connected [RuX6/2] octahedra. While in the chains of the hexagonal HT-forms the Ru-Ru-distances are identical (d(Ru-Ru) = 2.8275(10) A for beta-RuCl3, d(Ru-Ru) = 2.9425(6) A for RuBr 3), in the orthorhombic structures the chains are distorted through pairing of the ruthenium(III) atoms (d(Ru-Ru) = 2.6328(14) A / 3.0010(15) A for beta-RuCl3 at 170(3) K, d(Ru-Ru) = 2.765(1) A / 3.108(1) A for RuBr3 at 293(2) K). The hexagonal metric with a/c= ?3 holds also for the orthorhombic LT-forms. Large crystals and the final products of the phase transition from HT- to LT-forms are pseudomerohedral twins of three twin domains with nearly equal amounts complicating proof and analysis of the LT-forms.

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