1-Sep-2021 News Extracurricular laboratory:new discovery of Cis-Dichlorobis(2,2′-bipyridine)ruthenium(II)

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We report the synthesis of a new ligand, 4,4?-bis(3,5-dimethoxyphenyl)-6,6?-dimethyl-2,2?-bipyridine, optimised for binding to copper(I) and with pendant functionality that can eventually be developed into metallodendritic structures. The synthesis and photophysical properties of complexes with copper(I) and ruthenium(II) are reported. The solid state structure of the complex [Cu(1)2][PF6] · MeCN (1 = 4,4?-bis(3,5-dimethoxyphenyl)-6,6?-dimethyl-2,2?-bipyridine) is also 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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Two ruthenium(ii) polypyridyl complexes, [Ru(bpy)2(ptpn)] 2+ (1) (bpy = 2,2?-bipyridine, ptpn = 3-(1,10-phenanthroline-2- yl)-as-triazino[5,6-f]1,10-phenanthroline) and [Ru(phen)2(ptpn)] 2+ (2) (phen = 1,10-phenanthroline), were synthesized and characterized. Crystal structure analysis shows that complex 1 has a large planar aromatic area and possesses the potential to fit the geometric structure of G-quadruplex. The interaction of the G-quadruplex DNA with Ru(ii) complexes was explored by means of circular dichroism (CD), fluorescence resonance energy transfer (FRET) melting assay, competitive FRET assay and polymerase chain reaction (PCR) stop assay. The results indicated that complexes 1 and 2 both have the ability to promote the formation and stabilization of the human telomeric d[(TTAGGG)n] (HTG22) quadruplex and exhibit high G-quadruplex DNA selectivity over duplex DNA. The telomere repeat amplification protocol (TRAP) assay and long-term proliferation experiments further demonstrate that the Ru(ii) complexes are potent telomerase inhibitors and HeLa cell proliferation inhibitors. The Royal Society of Chemistry 2013.

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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 quality of emission spectra of metal complexes gives good insights into their performance in many optoelectronic applications. Herein, the effect of the number and position of various ligand structures on the emission spectra of Ru bipyridine complexes was studied. Specifically, the use of a different number of withdrawing groups (COOH) was investigated in detail. The complexes were first investigated using density functional theory (DFT) and time-dependent DFT calculations and then confirmed experimentally. The bandgap energy, reactivity, emission spectra and Stokes shift were found to depend on the number and position of the withdrawing groups attached to the Ru(bpy)22+ complexes. Upon increasing the number of withdrawing groups, the electrons were found to be withdrawn from the carbon orbitals and resonated to reach the metal, and accumulated around it, thus enhancing the metal-to-ligand charge transfer mechanism instead of the ligand-to-ligand charge transfer mechanism. The complexes with more withdrawing groups showed spectra with more intense emission peaks with shorter lifetime, indicating the enhancement in the photoactivity of the complexes. Ligands with ring nitrogens with two COOH groups showed the greatest effect on the enhancement of the emission spectra with a lifetime of 0.5359 ns. The resulting collective emission spectra covered a wide wavelength range, making the investigated complexes a good choice for many optoelectronic applications.

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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 series of complexes of the type <(bpy)2RuIIL-(Pro)n-CoIII(NH3)5>4+, n = 1-6, where L = 4-carboxy-4′-methyl-2,2′-bipyridine, bpy = 4,4′-bipyridine, and Pro = l-proline, have been synthesized from the corresponding <(bpy)2RuIIL> and <(NH3)5CoIII(Pro)n> components.The compounds were characterized by metal analyses, electrochemical measurements, and absorption spectroscopy.For n = 4-6 prolines, the CD spectra of the complexes show a polyproline II helical structure.Intramolecular electron transfer within these complexes was studied by generating the <(bpy)2uIIL.-(Pro)n-CoIII(NH3)5> intermediate by the reaction of eaq (generated by pulse radiolysis) with the <(bpy)2RuIIL-(Pro)n-CoIII(NH3)5> molecules.The driving force for this reaction is estimated to be ca. -1.1 V.The intramolecular electron transfer rates (k) and activation parameters (DeltaH<*> (kcal/mol, DeltaS<*> (eu) found for these studies were (1.6 +/- 0.1 x 107 s-1, 6.0 +/- 0.6, -6 +/- 2; (2.3 +/- 0.2) x 105 s-1, 9.2 +/- 0.4, -3 +/- 1; (5.1 +/- 0.4) x 104 s-1, 9.4 +/- 0.2, -5.5 +/- 0.8; (1.8 /- 0.1) x 104 s-1, 9.0 +/- 0.4, -9 +/- 1; and (8.9 +/- 0.6) x 103 s-1, 8.8 +/- 0.4, -11 +/- 1 for n = 2-6, respectively.For n = 1 proline, k is > 5 x 108 s-1 and no temperature dependence could be determined.The rate of intramolecular electron transfer decrease rapidly with distance for n = 1-3 prolines but show a surprisingly weak decrease with distance for the n = 4, 5, and 6 prolines, which exhibit the polyproline II helical structure.The electron-transfer pathways within these molecules and the relationship of the electron-transfer rates to the helical polyproline II structure are discussed.

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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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Changes in pH have been used to shift the band-edge positions of n-type ZnO electrodes relative to solution-based electron acceptors having pH-independent redox potentials. Differential capacitance vs. potential and current density vs. potential measurements using [Co(bpy)3]3+/2+ and [Ru(bpy)2(MeIm)2]3+/2+ (where bpy = 2,2?-bipyridyl and MeIm = 1-methyl-imidazole) allowed investigation of the pH-induced driving-force dependence of the interfacial electron-transfer rate in the normal and inverted regions of electron transfer, respectively. All rate processes were observed to be kinetically first-order in the concentration of electrons at the ZnO surface and first-order in the concentration of dissolved redox acceptors. Measurements using [Co(bpy)3]3+/2+, which has a low driving force and a high reorganization energy in contact with ZnO electrodes, and measurements of [Ru(bpy)2(MeIm)2]3+/2+, which has a high driving force and a low reorganization energy in contact with ZnO electrodes, allowed for the evaluation of both the normal and inverted regions of interfacial electron-transfer processes, respectively. The rate constant at optimum exoergicity was observed to be approximately 5 × 10-17 cm4 s-1. The rate constant vs. driving-force dependence at n-type ZnO electrodes exhibited both normal and inverted regions, and the data were well-fitted by parabolas generated using classical electron-transfer theory.

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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 molecular structure of an o-phenylenediamine unit-containing oligophenylene (1), Ph-Ph?-Ph?(2,3-NH2)-Ph?-Ph (Ph = phenyl; Ph? = p-phenylene; Ph?(2,3-NH2) = 2,3-diamino-p-phenylene), was determined by X-ray crystallography. 1 has a twisted structure, and forms an intermolecular C-H?pi interaction network. The -NH2 group of 1 was air-oxidized to an imine, {double bond, long}NH, group in the presence of [RuCl2(bpy)2] (bpy = 2,2?-bipyridyl) and gave a ruthenium(II)-benzoquinone diimine complex [Ru(2)(bpy)2](PF6)2 (2: Ph-Ph?-Ph?(2,3-imine)-Ph?-Ph). The molecular structure of [Ru(2)(bpy)2](PF6)2 was confirmed by X-ray crystallography. [Ru(2)(bpy)2](PF6)2 underwent two-step electrochemical reduction with E1/2 = -0.889 V and -1.531 V versus Fc+/Fc. The E1/2’s were located at higher potentials by 91 mV and 117 mV, respectively, than those of reported [Ru(bqdi)(bpy)2](PF6)2 (bqdi = benzoquinone diimine). Electrochemical oxidation of [Ru(2)(bpy)2](PF6)2 occurred at a lower potential by 180 mV than that of [Ru(bqdi)(bpy)2](PF6)2. Occurrence of the easier reduction and oxidation of [Ru(2)(bpy)2](PF6)2 than those of [Ru(bqdi)(bpy)2](PF6)2 is ascribed to the presence of a large pi-conjugation system in 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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Amide functionalized bipyridine ligands and their ruthenium(II) complexes of the type [Ru(bipyridine)2(L)](PF6)2 were synthesized and characterized by UV/Visible, emission, FTIR, 1H NMR spectroscopies and elemental analysis. Thermal properties of the ruthenium(II) polypyridyl complexes have been investigated using thermogravimetric analysis (TGA) and differential thermal analysis (DTA) techniques. These complexes show remarkable thermal stability at high temperatures under nitrogen atmosphere. The ruthenium(II) complexes show increasing fluorescence intensity in the presence of the amide groups. The increase of the emission intensity and quantum yield of the molecules may be attributed to the change of dipole moment of the amide group on electronic excitation. The effects of substituent (-CH3, -OCH3, -COOC2H5, -COOH) on photophysical properties of molecules were correlated with the Hammett Substituent Constants. The molecules exhibit linear correlation for absorption and emission maxima.

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

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A new cycloruthenated 2-(2-thienyl)pyridine complex (1) with a benzo[e]indolium block was successfully synthesized and characterized, which has good water-solubility and displays a maximum absorption band centered at 730 nm (epsilon = 6.3 × 103 M?1 cm?1) in water. Moreover, its absorption edge can extend to 1000 nm. When either HSO3 ? or SO3 2? ions were added to the buffer solutions of 1, obvious color changes from dark-red to purplish-red were observed. However, it is noticeable that the addition of HSO3 ? ions resulted in the solution color of this complex changing from dark-red to colorless other than purplish-red. The different solution color changes displayed that 1 can be used as an optical chemo-sensor to distinguish HSO3 ? from SO3 2? in pure water.

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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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There is great interest in the catalytic photoreduction of water to give hydrogen as a fuel to harness solar energy and a series of ruthenium complexes has been synthesized and tested as photosensitizers in this photoreduction process. There are very few precedents for N-heterocyclic carbene complexes in this field. The complexes obtained in this work were of the type [Ru(:C?N?C:)2](PF6)2 and [Ru(N?C:)3](PF6)2 with N-heterocyclic carbene ligands derived from pyridine and imidazole heterocycles with methyl or benzyl substituents. The photophysical properties of the complexes were studied. Some complexes were luminescent and, although the quantum yields were rather low, the lifetimes were quite high (1.5?1.7 mus). The emissive complexes behave as photosensitizers in the generation of H2 using [Co(bpy)3]Cl2 (bpy = 2,2?-bipyridine) as catalyst and triethanolamine (TEOA) as the sacrificial reductant through an oxidative quenching mechanism. The amount of hydrogen obtained was higher for the benzyl derivative.

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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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Surface-initiated, oligomeric assemblies of ruthenium(II) vinylpolypyridyl complexes have been grown within the cavities of mesoporous nanoparticle films of TiO2 by electrochemically controlled radical polymerization. Surface growth was monitored by cyclic voltammetry as well as UV/Vis and X-ray photoelectron spectroscopy. Polymerization occurs by a radical chain mechanism following cyclic voltammetry scans to negative potentials where reduction occurs at the pi* levels of the polypyridyl ligands. Oligomeric growth within the cavities of the TiO2 films occurs until an average of six repeat units are added to the surface-bound initiator site, which is in agreement with estimates of the internal volumes of the pores in the nanoparticle films.

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