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Efficient catalytic synthesis of tertiary and secondary amines from alcohols and urea

Urea as a nitrogen source: The supported ruthenium hydroxide, Ru(OH) x/ZTiO2, acts as an efficient heterogeneous catalyst for the title reaction. The retrieved catalyst after the reaction could be reused without a significant loss of its catalytic performance.

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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 new D-pi-D type Schiff base ligands and its complexes with Cobalt(II), Ruthenium(II)

A Schiff base ligands, N-no)phenyl]prop-2-en-1-ylidene}-1,10-phenanthrolin- 5-amine(mpa) and (1E,2E)-3-[4-(dimethylamino)phenyl]acrylaldehyde9H-fluoren-9- ylidenehydrazone(mfh), have been synthesized from the reaction of 4,5-diazafluorenone-9-hydrazone and 5-amino-1,10-phenanthroline with 4-(dimethylamino)cinnamaldehyde. The Co(II) and Ru(II) complexes of the ligands were prepared and characterized. The metal-to-ligand ratio of the Co(II) complex was found to be 2: 1 and that of the Ru(II) complex was found to be 1: 1. The ligands and complexes have been characterized by FTIR, UV-visible, 1H NMR and fluorescence spectra, as well as, elemental analyses, TGA-DSC-DTG and mass spectra.

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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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Comparison of inverse and regular 2-Pyridyl-1,2,3-triazole “click” Complexes: Structures, Stability, Electrochemical, and Photophysical Properties

Two inverse 2-pyridyl-1,2,3-triazole “click” ligands, 2-(4-phenyl-1H-1,2,3-triazol-1-yl)pyridine and 2-(4-benzyl-1H-1,2,3-triazol-1-yl)pyridine, and their palladium(II), platinum(II), rhenium(I), and ruthenium(II) complexes have been synthesized in good to excellent yields. The properties of these inverse “click” complexes have been compared to the isomeric regular compounds using a variety of techniques. X-ray crystallographic analysis shows that the regular and inverse complexes are structurally very similar. However, the chemical and physical properties of the isomers are quite different. Ligand exchange studies and density functional theory (DFT) calculations indicate that metal complexes of the regular 2-(1-R-1H-1,2,3-triazol-4-yl)pyridine (R = phenyl, benzyl) ligands are more stable than those formed with the inverse 2-(4-R-1H-1,2,3-triazol-1-yl)pyridine (R = phenyl, benzyl) “click” chelators. Additionally, the bis-2,2?-bipyridine (bpy) ruthenium(II) complexes of the “click” chelators have been shown to have short excited state lifetimes, which in the inverse triazole case, resulted in ejection of the 2-pyridyl-1,2,3-triazole ligand from the complex. Under identical conditions, the isomeric regular 2-pyridyl-1,2,3-triazole ruthenium(II) bpy complexes are photochemically inert. The absorption spectra of the inverse rhenium(I) and platinum(II) complexes are red-shifted compared to the regular compounds. It is shown that conjugation between the substituent group R and triazolyl unit has a negligible effect on the photophysical properties of the complexes. The inverse rhenium(I) complexes have large Stokes shifts, long metal-to-ligand charge transfer (MLCT) excited state lifetimes, and respectable quantum yields which are relatively solvent insensitive.

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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 panchromatic Ru(II) thienyl-dipyrrin complexes and evaluation of their light-harvesting capacity

Ru(II) complexes with 5-(3-thienyl)-4,6-dipyrrin (3-TDP), containing 2,2?-bipyridine (bpy) or 4,4?-bis(methoxycarbonyl)-2,2?- bipyridine (dcmb) as coligands, have been prepared and extensively characterized. Crystal structure determination of [Ru(bpy)2(3-TDP)] PF6 (1a) and [Ru(bpy)(3-TDP)2] (2) reveals that the 3-thienyl substituent is rotated with respect to the plane of the dipyrrinato moiety. These complexes, as well as [Ru(dcmb)2(3-TDP)]PF6 (1b), act as panchromatic light absorbers in the visible range, with two strong absorption bands observable in each case. A comparison to known Ru(II) complexes and quantum-chemical calculations at the density functional theory (DFT) level indicate that the lower-energy band is due to metal-to-ligand charge transfer (MLCT) excitation, although the frontier occupied metal-based molecular orbitals (MOs) contain significant contributions from the 3-TDP moiety. The higher energy band is assigned to the pi-pi* transition of the 3-TDP ligand. Each complex exhibits an easily accessible one-electron oxidation. According to DFT calculations and spectroelectrochemical experiments, the first oxidation takes place at the RuII center in 1a, but is shifted to the 3-TDP ligand in 1b. An analysis of MO energy diagrams suggests that complex 1b has potential to be used for light harvesting in the dye-sensitized (Graetzel) solar cell.

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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 Dual Killing Strategy: Photocatalytic Generation of Singlet Oxygen with Concomitant PtIV Prodrug Activation

A ruthenium-based mitochondrial-targeting photosensitiser that undergoes efficient cell uptake, enables the rapid catalytic conversion of PtIV prodrugs into their active PtII counterparts, and drives the generation of singlet oxygen was designed. This dual mode of action drives two orthogonal cancer-cell killing mechanisms with temporal and spatial control. The designed photosensitiser was shown to elicit cell death of a panel of cancer cell lines including those showing oxaliplatin-resistance.

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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 RuII Polypyridyl Alkyne Complex Based Metal?Organic Frameworks for Combined Photodynamic/Photothermal/Chemotherapy

Despite drug delivery nanoplatforms receiving extensive attention, development of a simple, effective, and multifunctional theranostics nanoplatform still remains a challenge. Herein, a versatile nanoplatform based on a zirconium framework (UiO-66-N3) was synthesized, which demonstrated a combined photodynamic therapy (PDT), photothermal therapy (PTT), and chemotherapy (CT) for cancer treatment. A RuII polypyridyl alkyne complex (Ra) as a photosensitizer was modified into a nanoplatform by click reactions for the first time. When exposed to suitable light irradiation, the as-prepared multifunctional nanoplatform (UiO-Ra-DOX-CuS) not only demonstrated efficient 1O2 generation, but also exhibited excellent photothermal conversion ability. In particular, the nanotherapeutic agent presented a dual-stimuli response; either acidic environment or NIR laser irradiation would trigger the drug release. The synergetic efficacy of UiO-Ra-DOX-CuS combined PDT, PTT, and CT, which was evaluated by cell experiments. Moreover, the design could promote the development of RuII polypyridyl alkyne complexes based multifunctional nanoparticles and multimodal cancer treatment.

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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 new organometallic synthon in diamondoid crystal engineering?

The cubane-type cation [{Ru(eta6-C6H6)(mu3-OH)} 4]4+ (1) exhibits a tetrahedrally arranged set of four strong hydrogen bond donor groups but has essentially no hydrogen bond acceptor properties. As a result counter anions with even weak hydrogen bond acceptor properties must exhibit a tetrahedral arrangement about the cation. In the case of anions able to non-covalently bridge between pairs of cations (e.g. dianions) this will result in a diamondoid lattice.

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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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Heterobimetallic Ru(mu-dppm)Fe and homobimetallic Ru(mu-dppm)Ru complexes as potential anti-cancer agents

Two heterobimetallic mu-dppm bridged Fe,Ru complexes, [(eta6-Arene)RuCl2(mu-dppm)Fe(CO)I(eta5-C5H5)] (Ar = C6H6 (1) and p-cymene (2), dppm = 1,1-bis(diphenylphosphino)methane) were obtained in a facile reaction between [Fe(eta5-C5H5)I(CO)(kappa1-dppm)] (5) and the corresponding [(eta6-Arene)RuCl2]2 complexes by dimer cleavage, mediated by the pendant -PPh2 in 5. The homodinuclear Ru,Ru complex, [(eta6-C6H6)RuCl2(mu-dppm)RuCl2(eta6-C6H6)] (3), was also isolated in a straightforward fashion upon reaction of [(eta6-C6H6)RuCl2(kappa1-dppm)] (4) with [(eta6-C6H6)RuCl2]2. All complexes were fully characterized by multinuclear (1H, 13C{1H}, 31P{1H}) NMR, UV?Vis, IR spectroscopy and HRMS (ESI), and additionally complex 3 was characterized by single crystal X-ray diffraction. Density functional theory (DFT) calculations (Level of theory B3LYP, basis set for H, C, P, O, N and Cl is 6-31 + G(d,p) and for Ru,Fe DGDZVP) of 1, 2 and 3 are also reported. Complexes 1 and 2 feature HOMOs and LUMOs delocalized over the iron-centered terminus of the bimetallic complexes. The cytotoxicity of 1?5 were evaluated on A2780 and A2780cisR (Human ovarian carcinoma) cell lines and the HEK293 (Human embryonic kidney) cell line. The complexes containing iron are more cytotoxic than cisplatin in the A2780 cells and significantly more active in the A2780cisR cell line and exhibit some selectivity towards the cancer cells. The dinuclear Ru,Ru complex 3 and the mononuclear complex 4 exhibit moderate activity on A2780 and A2780cisR cells also with some cancer cell selectivity. This study hence reveals the potential of Fe,Ru complexes as potent cytotoxic agents.

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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, molecular, crystal and electronic structure of [(C6H6)RuCl(1,10-C12H8N2)]Cl

The [(C6H6)RuCl(1,10-C12H8N2)]Cl complex has been prepared and studied by IR, UV-Vis, 1H NMR spectroscopy and X-ray crystallography. The complex was prepared in reaction of [(C6H6)RuCl2]2 with 1,10-phenatroline in acetone. The electronic spectrum of the compound has been calculated using the TDDFT method.

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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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Intramolecular Electron Transfer in Linked Tris(2,2′-bipyridine)ruthenium(II)/Diquat Complexes

Electron transfer (ET) rates have been measured for a series of linked tris(2,2′-bipyridine)ruthenium(II)/diquat complexes in room-temperature acetonitrile solutions, using time-resolved picosecond emission and absorption spectroscopies.The rate of ET from the metal-to-ligand charge transfer (MLCT) states to the diqaut acceptor has been analyzed in terms of a simple kinetic model, in which MLCT exciton hopping is fast, ET to the diquat is rate limiting, and the latter occurs only from MLCT states localized on bipyridine ligands which are linked to diquat acceptors.Electrochemical data for Ru 2+/1+ and Ru 1+/0 reduction potentials have been related to MLCT state energies and used in the model.Semiquantitative agreement was found between the model’s predictions and measured ET times.A linear relationship was found to exist between ET driving force and the log of the ET rate.Reverse (diqaut to ruthenium) ET rates were determined to be fast relative to forward rates.

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