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Two molecular assemblies with one Ru(II)-polypyridine photosensitizer covalently linked to one Ru(II)(bda)L2 catalyst (1) (bda = 2,2?-bipyridine-6,6?-dicarboxylate) and two photosensitizers covalently linked to one catalyst (2) have been prepared using a simple C-C bond as the linkage. In the presence of sodium persulfate as a sacrificial electron acceptor, both of them show high activity for catalytic water oxidation driven by visible light, with a turnover number up to 200 for 2. The linked photocatalysts show a lower initial yield for light driven oxygen evolution but a much better photostability compared to the three component system with separate sensitizer, catalyst and acceptor, leading to a much greater turnover number. Photocatalytic experiments and time-resolved spectroscopy were carried out to probe the mechanism of this catalysis. The linked catalyst in its Ru(II) state rapidly quenches the sensitizer, predominantly by energy transfer. However, a higher stability under photocatalytic condition is shown for the linked sensitizer compared to the three component system, which is attributed to kinetic stabilization by rapid photosensitizer regeneration. Strategies for employment of the sensitizer-catalyst molecules in more efficient photocatalytic systems are discussed.

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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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Two mononuclear ruthenium complexes [(bpy)2RuIIL1/L2](ClO4)2 ([1]2+/[2]2+) (bpy-2,2? bipyridine, L1 = 2,3-di(pyridin-2-yl)pyrazino[2,3-f][1,10]phenanthroline) and L2 = 2,3-di(thiophen-2-yl)pyrazino[2,3-f][1,10]phenanthroline have been synthesized. The complexes have been characterized using various analytical techniques. The complex [1]2+ has further been characterized by its single crystal X-ray structure suggesting ruthenium is coordinating through the N donors of phenanthroline end. Theoretical investigation suggests that the HOMOs of both complexes are composed of pyridine and pyrazine unit of ligands L1 and L2 whereas the LUMOs are formed by the contribution of bipyridine units. The low energy bands at ?480 nm of the complexes can be assigned as MLCT with partial contribution from ligand transitions, whereas the rest are ligand centered. The complexes have shown RuII/RuIII oxidation couples at E1/2 at 1.26 (70 mV) V and 1.28 (62 mV) V for [1]2+ and [2]2+ vs Ag/AgCl, respectively, suggesting no significant role of distal thiophene or pyridine units of the ligands. The complexes are emissive and display solvent dependent emission properties. Both complexes have shown highest emission quantum yield and lifetime in DMSO (? = 0.05 and tauavg = 460 ns and lambdamaxem at 620 nm for [1]2+; ? = 0.043 and tauavg = 425 ns and lambdamaxem at 635 nm for [2]2+). Further, the long luminescent lifetime of these complexes has been utilized to generate reactive oxygen species for efficient azo dye decomposition.

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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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We have investigated the electrochemical, spectroscopic and electroluminescent properties of a family of aza-aromatic complexes of ruthenium of type [RuII(bpy/phen)2(L)]2+ (4d6) with three isomeric L ligands, where, bpy = 2,2?-bipyridine, phen = 1,10-phenanthroline and the L ligands are 3-(2-pyridyl)[1,2,4]triazolo[1,5-a]pyridine (L1), 3-(2-pyridyl[1,2,3])triazolo[1,5-a]pyridine (L2) and 2-(2-pyridyl)[1,2,4]triazolo[1,5-a]pyridine (L3). The complexes display two bands in the visible region near 410-420 and 440-450 nm. The complexes are diamagnetic and show well defined 1H NMR lines. They are electroactive in acetonitrile solution and exhibit a well defined RuII/RuIII couple near 1.20 to 1.30 V and -1.40 to -1.50 V due to ligand reduction versus Saturated Calomel Electrode (SCE). The solutions are also luminescent, with peaks are near 600 nm. All the complexes are electroluminescent in nature with peaks lying near 580 nm. L1 and L3 ligated complexes with two bpy co-ligands show weak photoluminescence (PL) but stronger electroluminescence (EL) compared to corresponding L2 ligated analogues.

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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 chemically functionalized nanocrystalline TiO2 grafted ruthenium(ii) polyazine complex was found to be an efficient visible light photoredox catalyst for the oxidative cyanation of tertiary amines to the corresponding alpha-aminonitriles in high to excellent yields, using molecular oxygen as an oxidant and sodium cyanide in acetic acid as a cyanide source. The developed photoredox catalyst could be easily recovered by simple filtration and reused for several runs with consistent catalytic activity.

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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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We report a sustainable in vitro system for enzyme-based photohydrogen production. The [FeFe]-hydrogenase HydA1 from Chlamydomonas reinhardtii was tested for photohydrogen production as a proton-reducing catalyst in combination with eight different photosensitizers. Using the organic dye 5-carboxyeosin as a photosensitizer and plant-type ferredoxin PetF as an electron mediator, HydA1 achieves the highest light-driven turnover number (TONHydA1) yet reported for an enzyme-based in vitro system (2.9×106 mol(H2) mol(cat)?1) and a maximum turnover frequency (TOFHydA1) of 550 mol(H2) mol(HydA1)?1 s?1. The system is fueled very effectively by ambient daylight and can be further simplified by using 5-carboxyeosin and HydA1 as a two-component photosensitizer/biocatalyst system without an additional redox mediator.

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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 invention discloses a novel ruthenium complex and a preparation method thereof and a method 5 – for detecting, formyl cytosine in, formyl cytosine, and the ruthenium complex can specifically recognize 5 – which has good fluorescence response and chemical stability . and the ruthenium complex can be used for detecting 5 -formyl cytosine in real time and carrying out distribution and positioning, on the double strand DNA in real time and carrying out distribution and positioning in cells 5fC . The present invention further provides a novel ruthenium complex and a preparation method of the ruthenium complex in the detection method of the cytosine DNA shown in 5fC, The invention further provides a novel 5fC ruthenium complex and a preparation method of the ruthenium complex in the, preparation method of, the novel 5 – ruthenium complex and preparation, thereof, The present invention further provides, a novel ruthenium complex and, a preparation method of the ruthenium complex in the preparation method of the novel ruthenium complex, and is suitable for detecting, formyl cytosine. DNA. (by machine translation)

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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 electronic spectra of 4 cyclometalated ruthenium compounds built up from cycloruthenated 2-phenylpyridine with monodentate and bidentate ligands, namely 1 [Ru(MeCN)2(phen)(PhPy)]1+ (RDC11), 2 [Ru(phen)2(PhPy)]1+ (RDC34), 3 [Ru(MeCN) 2(PhPy)(dppz)]1+ (RDC11Z), 4 [Ru(bpy)(PhPy)(dppz)] 1+ (RDCbpZ), the last two being newly synthesized, have been recorded and calculated together with that of 5 [Ru(bpy)2(dppz)]2+ (RDNbpZ). Recently synthesized variants of RDC34 where the phenylpyridine ligand is substituted with an electro-attractor or an electro-donor group, 6 [Ru(phen)2(NO2PhPy)]1+ RDC40 and 7 [Ru(phen)2(NH2PhPy)]1+ RDC41 respectively, and the dicationic reference complex [Ru (phen)2(bpy)]2+ (RDN34) have been investigated as well for comparison. The global structures of RDC34 and RDN34 are very similar despite of the substitution of one N atom by one C atom. As expected a shortening of the Ru-C bond as compared to the Ru-N bond is observed. The calculated structures of the investigated complexes point to a rather rigid structure whatever their environment. The introduction of a strong Ru-C bond has a minor effect on the coordination sphere around the metal atom keeping the other Ru-N bonds and bond angles similar, the only noticeable alteration being an increase of the Ru-N bond trans to the Ru-C bond. The experimental spectra are characterized by an intense band in the UV domain centered at 270 nm and corresponding to a strong intra-ligand (IL) absorption. Low-lying MLCT states contribute to a weak shoulder around 370 nm and to a large band between 550 nm and 400 nm. The tail of this band, towards 650 nm, is a characteristic of the cyclometalated complexes. This series of molecules, as other polypyridyl complexes, are characterized by a high density of excited states in the vis/UV energy domain, a large mixing between MLCT/IL and LLCT states in the upper part of the spectrum, and a significant sensitivity to the environment of the IL state localized on the dppz 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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The applicability of RuII polypyridyl complexes with appropriate functionalities as substrates for biorthogonal coupling reactions is investigated. In detail, copper(I)-catalyzed azide?alkyne cycloadditions (CuAAC), strain-promoted azide?alkyne cycloadditions (SPAAC), and maleimide?thiol coupling reactions of ruthenium complexes are examined. The first examples of SPAAC in which the organic azide is provided by the metal complex are presented. All of the chromophores belong to one easy-to-synthesize scaffold, which has proven to be convenient for the application of metal chromophores. The fundamental photophysical properties of the examined compounds do not change with substitution, which is important for the design of chromophore conjugates. Furthermore, the limitations of CuAAC reactions will be discussed with regard to copper impurities in the products formed.

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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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Synthetic routes were developed to attach three redox-active metal fragments to cross-conjugated 3-methylidenepentadiyne covalently expanded by diazafluorenylidene: The two alkyne termini of this new ligand were end-capped via a phenylene spacer with ethynyl ferrocene, and a [Ru(bpy)2]2+ fragment was coordinated in the diimine binding site. The photophysical and electrochemical properties of both the diferrocenyl-terminated ligand and its corresponding Ru-complex were investigated by UV-vis absorption spectroscopy and cyclic voltammetry. The absorption data reveal significant interactions of the metal centers with the cross-conjugated ligand system. In the electrochemical experiments the ferrocenyl and the ruthenium centers could be addressed individually as they are separated by almost 1 V. While the presence of the Ru-fragment manifests itself in the reduction potential of the diazafluorenylidene-ligand, communication between the ferrocenyl end-caps on one hand and between the ferrocenes and the Ru-fragment on the other appears to be reduced through the freely rotating phenylene spacers.

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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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Because of their unique cyclic architectures, tunable electronic properties, and supramolecular chemistries, cycloparaphenylenes (CPPs) have the potential to act as a new class of ligands for coordination cages, metal-organic frameworks, and small-molecule transition-metal complexes. However, currently there is no general strategy to coordinate the cyclic framework to a variety of metal centers. We report here a general and scalable synthetic strategy to embed 2,2?-bipyridine units into the backbone of CPPs. We use this approach to synthesize a 2,2?-bipyridine-embedded [8]CPP, which we show can successfully coordinate to both Pd(II) and Ru(II) metal centers. The resulting coordination complexes, a Pd(II)-nanohoop dimer and a bis(bipyridyl)ruthenium(II)-functionalized nanohoop, show unique solid-state and photophysical properties. This work provides a proof of concept for a general strategy to use nanohoops and their derivatives as a new class of ligands.

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