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We performed measurements of magnetic susceptibility, electrical resistivity, and magnetoresistance in magnetic fields of up to 18 T in the magnetic superconductor RuGd1.4Ce0.6Sr2Cu2O10 – delta synthesized in oxygen pressures up to 95 atm. The magnetic-susceptibility data show the occurrence of an antiferromagnetic state below TN? 175 K, followed by the development of a weak ferromagnetic state near TM ? 100 K, and followed further by the onset of superconductivity (SC) at Tc ? 42 K. The electrical resistivity as a function of temperature shows an evolution from nonmetal-to-SC behavior in samples prepared in a flux of O2 to a well defined metal-like behavior in samples prepared under 95 atm pressure of O2. The electron-phonon coupling constant was calculated from transport data to be lambdatr?0.17, a value comparable with other cuprates, indicating weak electron-phonon coupling in these ruthenates. The values of the upper critical field Hc2 for the O2 high-pressure treated samples were obtained from the magnetoresistivity data yielding Hc2ab(0)?39 T, and the out-of-plane superconducting coherence length xic(0) ? (0) ? 28 A . Based on the similarities between these ruthenates and the superconductor YBa2Cu3O7 – delta, we estimated Hc2c(0) ? 8 T and xiab(0) ? 140 A . We used these parameters to discuss the coexistence of long-range magnetic order and superconductivity on a microscopic scale on these materials.

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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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As part of our efforts to develop ruthenium nitrosyl compounds for use as nitric oxide delivery agents, a new six coordinate {RuNO}6 compound, [Ru(NO)(bpb)Cl] (bpb = N,N?-bis(2-pyridinecarboxamide)-1,2-benzene dianion) was prepared from the reaction between [Ru(NO)Cl(H2O) 2] and N,N?-bis(2-pyridine carboxamide)-1,2-benzene. We report here the characterization of this new compound by 1H, 13C, HH COSY, HMQC and HMBC NMR spectroscopy, IR spectroscopy (nuNO = 1867 cm-1) and ESI-MS (M + Na+ 505.9).

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

Some scientific research about Ruthenium(III) chloride

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Two new heteroleptic ruthenium(ii) photosensitizers that contains 2,2?;6,2??-terpyridine with extended pi-conjugation with donor groups, a 4,4?-dicarboxylic acid-2,2?-bipyridine anchoring ligand and a thiocyanate ligand have been designed, synthesized and fully characterized by CHN, mass spectrometry, UV-vis and fluorescence spectroscopies and cyclic voltammetry. The new sensitizers have either 3,5-di-tert-butyl phenyl (m-BL-5) or triphenylamine (m-BL-6) groups, where the molar extinction coefficient of both the sensitizers is higher than the analogous ruthenium dyes. Both the sensitizers were tested in dye-sensitized solar cells using two different redox electrolytes.

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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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Complex bimetallic salts of the type [M(L-L)3[M'(MNT)2] [M=Ni(II), Zn(II), Cd(II), Fe(I]), Co(II), Cu(II) and Ru(II); M’ = Ni(II) and Co(II); L-L = 2,2′-bipyridyl (bipy) ; 1,10-phenanthroline (o-phen) or ethylenediamine (en); MNT = 1,2-dicyano-1,2-ethylenedithiolate] have been prepared by the reaction of Na2[M'(MNT)2] and [M(L-L)3]X2. These Salts have been characterized by elemental analyses, molar conductance, magnetic susceptibility, IR and UV-visible spectral studies. X-ray diffraction patterns indicate their non-isomorphous nature. All the complexes behave as semiconductors as their solid-state conductivities were found to increase with the increase in temperature from 305 to 393 K.

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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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This study examined the conversions, via oxidative fusion or coupling, of B5H81- to B10H14 and 2,2′-(B5H8)2 in the presence of FeCl2/FeCl3, of B5H81- to B10H14 alone in the presence of RuCl3, and of 1-XB5H71- (X = D and CH3) to 2,4-B10H12D2 and 2,2-(1-CH3B5H7)2 with RuCl3 or FeCl2/FeCl3.The B10H131- ion was shown to form n- and i-B18H22 on treatment with RuCl3 in THF and subsequent exposure to air.The RuCl3-promoted fusions of the square-pyramidal cobaltaboranes 2-(epsilon5-C5H5)CoB4H71- and 1-(epsilon5-C5H5)CoB4H71- (both analogues of B5H81- to give nido-(eta-C5H5)2Co2B8H12 isomers were also studied.The 2-isomer yields primarily 5,8-, 1,5-, and 1,7-(eta-C5H5)2Co2B8H12, while the 1-isomer affords only 2,4-(eta5-C5H5)2Co2B8H12.All these observations support a fusion mechanism in which two square-pyramidal substrate molecules, facilitated by coordination to a common metal ion, are initially joined at their basal edges and then complete the fusion process to give a nido 10-vertex cage in which the original apex (1-vertex) atoms become the 2,4-vertexes in the product.The new compounds were characterized via infrared, 11B and 1H NMR, mass spectra, and in some cases by two-dimensional (2D) 11B homonuclear NMR.

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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 authors report details of the synthesis of (Ru(OEP))//2 and (Ru(TPP))//2 and an analysis of the paramagnetic shifts observed in their proton NMR spectra. In addition, the X-ray crystallographic study of (Ru(OEP))//2 is described.

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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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Resonance Raman (RR) and optical spectroelectrochemical titrations of the cis,cis-[(bpy)2Ru-(OH2)]2O4+ ion (denoted [3,3] to indicate the formal oxidation state of the Ru-O-Ru unit) were made over the range 0.8-2.0 V vs Ag/AgCl in 0.5 M trifluoromethanesulfonic acid; the results revealed sequential accumulation of three higher oxidation states. Two of these states were identified by redox titration with Os(bpy)32+ as one-electron ([3,4]) and four-electron oxidized species ([5,5]); spectroscopic analysis of reaction products formed upon mixing the [3,3] and [5,5] ions indicated that the third oxidation state is a two-electron oxidized species ([4,4]). The [5,5] ion underwent first-order decay to the [4,4] ion with a rate constant, k ? 9.5 x 10-3 s-1, that was nearly identical with the catalytic turnover rate for O2 evolution, k(cat) ? 1.3 x 10-2 s-1 measured under comparable conditions. The [4,4] ion underwent degradation more slowly to the [3,4] ion, which was stable on these time scales. An analogue bearing 4,4′- dimethyl-2,2′-bipyridine ligands exhibited very similar behavior, except that the oxidation steps were shifted by ~50 mV to lower potentials. 18O isotope labeling experiments on the underivatized complex established that there was no oxygen exchange at the bridging mu-oxo position during catalytic turnover. Frozen solutions of the [5,5] ion displayed unusual low-temperature spectroscopic features, including the following: (i) a narrow g = 2.02 axial EPR signal exhibiting an apparent six-line hyperfine interaction from a minor component; (ii) a concentration-dependent broad rhombic EPR signal in mixtures also containing the [4,4] ion; and (iii) a concentration-dependent replacement of its characteristic ruthenyl Ru=O stretching mode at 818 cm-1 in the RR spectrum when chemically oxidized with Ce4+ by an 18O isotope sensitive set of three bands in the 650 cm-1 region. The RR spectrum of this new species is consistent with further coordination of the terminal oxo ligands by Ce4+ to form additional ligand bridges.

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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 2,2?:6?,2?-terpyridine bearing a closo-ortho-carboranyl substituent in the 4?-position has been prepared and structurally characterised (triclinic, P 1, a = 6.935(1). b = 12.062(1), c = 13.817(3) A, alpha = 107.827(13), beta = 102.532(13), gamma = 102.222(8), V = 1024.9(3) A3, R = 0.057, Rw = 0.065). Although the free ligand is stable in aprotic solvents, reaction with alcohols leads to the formation of an insoluble Zwitterionic nido-cluster-substituted ligand. A similar nuclearity change occurs upon coordination to ruthenium(II). The presence of a tert-butyldimethylsilyl protecting group on the carborane stabilises the cluster with respect to these nuclearity changes. CNRS-Gauthier-Villars.

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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 complex (1) undergoes a reversible one-electron oxidation at +0.77V vs. a saturated calomel electrode (s.c.e.) on a Pt electrode in 1,2-dichloroethane containing 0.1 mol dm-3 NBu4ClO4.A cyclic voltammetric study establishes that under a CO atmosphere, (1) is quantitatively converted into trans,trans,trans- (3) (E1/2 = +1.65 V) via (2) E1/2 =1.35 V).Complex (2) interconverts with (3) via reversible CO co-ordination.Regeneration of (1) from (3) requires u.v. irradiation in the presence of excess L.The reversible one-electron reduction of (4) occurs at -0.22 V.The structure of complex (4) was established by a single-crystal X-ray diffraction study.Crystals are orthorhombic, space group P212121 (no.19), with Z = 4 in a unit cell of dimensions a = 9.104(2), b = 15.511(2), and c = 24.190(2) Angstroem.The structure has been refined to R 0.034 (R’ 0.046).The Ru atom has a distorted octahedral environment with the three chlorine atoms in a mer relationship.The chelating ligand is characterized by a Ru-P(2) distance of 2.368(2) Angstroem and a relatively short Ru-O(3) distance of 2.143(5) Angstroem.The distance between Ru and the chlorine atom trans to the co-ordinated ester oxygen is 2.312(2) Angstroem whereas Ru-Cl(2) and Ru-Cl(3) are 2.323(2) and 2.362(2) Angstroem, respectively.

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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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Ruthenium(III) catalysed oxidation of substituted cinnamic acids by in aqueous acetic acid-sulphuric acid medium follows a complex rate law, the reaction being zero order in , first order in and fractional order in .Increase in the proportion of acetic acid in the reaction medium retards the reaction rate.The Hammett plot shows a break with rho values of -1.65 (electron-releasing groups) and 0.03 (electron-withdrawing groups).Activation parameters have been computed.A mechanism involving rate-determining rearrangement of the Ru(III)-substrate ?-complex to the ?-complex and its cleavage in a concerted manner has been suggested.

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