Category: 15746-57-3

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Transient photocyclization in ruthenium(II) polypyridine complexes of indolamines

Ruthenium polypyridine complexes have proved to be useful caging groups for visible-light photodelivery of biomolecules. In most photoreactions, one ligand is expelled upon irradiation, yielding ruthenium mono-aqua complexes and no other photoproduct. In this work we show that a long-lived transient photoproduct is generated when the ruthenium complexes involve indolamines. The spatial conformation of this species is compatible with a cyclic structure that contains both the amine and the normally non-coordinating aromatic ring coordinated to the ruthenium center.

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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 dinuclear ruthenium(II) complex linked via a reducible azo group [Ru(bpy)2(azobpy)Ru(bpy)2]Cl4 (Ru 2azo, bpy = 2,2?-bipyridine, azobpy = 4,4?-azobis (2,2?-bipyridine)) was adopted as a probe for thiols. Results showed that Ru2azo could selectively and effectively react with biological thiols (such as cysteine, homocysteine and glutathione) with a 10- 7 M detection limit. After it reacted with thiols, the original gray color of Ru2azo solution immediately turned yellow and the luminescence significantly enhanced, showing “naked-eye” colorimetric and “off-on” luminescent dual-signaling response for thiols. Mechanism studies demonstrated that Ru2azo reacted with thiols undergoing a two-electron transfer process, forming the azo2 – anion product.

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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 synthesized a number of dinuclear species containing both identical or different metal-based components by employing new bridging ligands having either aliphatic or aromatic spacers and taking advantage of the “complexes as metals and complexes as ligands” synthetic strategy. The bridging ligands are dpt-S-dpt (S is 1,4-cyclohexyl, 1,4-phenyl, 4,4?-biphenyl; dpt is 4-amino-3,5-bis(2-pyridyl)-1,2,4-triazole; the connections between S and dpt are provided by amide links). The complexes synthesized are: [(bpy)2Ru(dpt-S-dpt)Ru(bpy)2](PF6)4 (bpy=2,2?-bipyridine; biq=2,2?-biquinoline; S=1,4-cyclohexyl (1), 1,4-phenyl (4), 4,4?-biphenyl (7)); [(biq)2Ru(dpt-S-dpt)Ru(biq)2](PF6)4 (S=1,4-cyclohexyl (2), 1,4-phenyl (5), 4,4?-biphenyl (8)); [(bpy)2Ru( dpt-S-dpt )-Ru(biq)2](PF6)4 (S=1,4-cyclohexyl (3), 1,4-phenyl (6), 4,4?-biphenyl (9)). The absorption spectra, luminescence properties and redox behavior of all the compounds have been studied. In the complexes containing different metal-based components, photoinduced energy transfer occurs from the higher-lying Ru ? bpy CT level, centered on a metal subunit, to the lower-lying Ru ? biq CT excited state, centered on the other metal component. In fluid solution at room temperature, the energy transfer is suggested to be mediated by a two-step electron transfer mechanism, whereas direct energy transfer between the chromophores most likely occurs at 77 K in rigid matrix. At the moment we are not able to say if the energy transfer at 77 K takes place via electron exchange or coulombic mechanisms. The results obtained indicate that the efficiency of the processes depends on the donor-acceptor distance, as expected, and that occasional pi bonds which are present within the bridging ligands cannot be used for speeding up electron transfer in multicomponent systems if the main skeleton of the bridge is made by sigma bonds.

Balanced chemical reaction does not necessarily reveal either the individual elementary reactions by which a reaction occurs or its rate law.Recommanded Product: Cis-Dichlorobis(2,2′-bipyridine)ruthenium(II). In my other articles, you can also check out more blogs about 15746-57-3

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

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We have recently disclosed [(dtbpy)2RuCl2] as an effective precatalyst for chemoselective C-H hydroxylation of C(sp3)-H bonds and have noted a marked disparity in reaction performance between 4,4?-di-tert-butyl-2,2?-bipyridine (dtbpy)- and 2,2?-bipyridine (bpy)-derived complexes. A desire to understand the origin of this difference and to further advance this catalytic method has motivated the comprehensive mechanistic investigation described herein. Details of this reaction have been unveiled through evaluation of ligand structure-activity relationships, electrochemical and kinetic studies, and pressurized sample infusion high-resolution mass spectrometry (PSI-MS). Salient findings from this investigation include the identification of more than one active oxidant and three disparate mechanisms for catalyst decomposition/arrest. Catalyst efficiency, as measured by turnover number, has a strong inverse correlation with the rate and extent of ligand dissociation, which is dependent on the identity of bipyridyl 4,4?-substituent groups. Dissociated bipyridyl ligand is oxidized to mono- and bis-N-oxide species under the reaction conditions, the former of which is found to act as a potent catalyst poison, yielding a catalytically inactive tris-ligated [Ru(dtbpy)2(dtbpy N-oxide)]2+ complex. Insights gained through this work highlight the power of PSI-MS for studies of complex reaction processes and are guiding ongoing efforts to develop high-performance, next-generation catalyst systems for C-H hydroxylation.

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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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Eilatin, a marine alkaloid, is a potentially bifacial ligand that prefers to bind through its less hindered face in sterically demanding geometries as evident by the selective synthesis of two octahedral ruthenium complexes.

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

The reaction rate of a catalyzed reaction is faster than the reaction rate of the uncatalyzed reaction at the same temperature.15746-57-3, Name is Cis-Dichlorobis(2,2′-bipyridine)ruthenium(II), molecular formula is C20H16Cl2N4Ru. In a Article，once mentioned of 15746-57-3, Product Details of 15746-57-3

A novel polypyridine ruthenium(II)/osmium(II) heterobinuclear complex (2) was synthesized.The luminescence properties of 2 were compared with those of its component complex.In 2, the efficient intramolecular energy transfer from excited Ru(II) to Os(II) complex was observed and interpreted by Foerster mechanism.

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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 new family of ruthenium(II) complexes with sterically expansive ligands for targeting DNA defects was prepared, and their luminescent responses to base pair mismatches and/or abasic sites were investigated. Design of the complexes sought to combine the mismatch specificity of sterically expansive metalloinsertors, such as [Rh(bpy)2(chrysi)]3+ (chrysi = chrysene-5,6-quinone diimine), and the light switch behavior of [Ru(bpy) 2(dppz)]2+ (dppz = dipyrido[3,2-a:2′,3′-c]phenazine). In one approach, complexes bearing analogues of chrysi incorporating hydrogen-bonding functionality similar to dppz were synthesized. While the complexes show luminescence only at low temperatures (77 K), competition experiments with [Ru(bpy)2(dppz)]2+ at ambient temperatures reveal that the chrysi derivatives preferentially bind DNA mismatches. In another approach, various substituents were introduced onto the dppz ligand to increase its steric bulk for mismatch binding while maintaining planarity. Steady state luminescence and luminescence lifetime measurements reveal that these dppz derivative complexes behave as DNA “light switches” but that the selectivity in binding and luminescence with mismatched/abasic versus well-matched DNA is not high. In all cases, luminescence depends sensitively upon structural perturbations to the dppz ligand.

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

A catalyst don’t appear in the overall stoichiometry of the reaction it catalyzes, but it must appear in at least one of the elementary reactions in the mechanism for the catalyzed reaction. 15746-57-3, Name is Cis-Dichlorobis(2,2′-bipyridine)ruthenium(II), molecular formula is C20H16Cl2N4Ru. In a Article，once mentioned of 15746-57-3, HPLC of Formula: C20H16Cl2N4Ru

A series of artificial receptors, based on a sulfonamido system, have been designed and synthesized. The interaction of these receptors with biologically important anions was determined by UV-vis, 1H NMR titration and electrochemical experiments. Results indicate that these receptors show high recognition abilities for fluoride (F-) or acetate (AcO-), moderate affinities for dihydrogen phosphate (H2PO4 -) or hydroxyl (OH-) and almost no affinities for chloride (Cl-), bromide (Br-) or iodide (I-). 1H NMR titration shows that the interaction between the receptors and anions depends on the hydrogen-bond formation. The CoIII/Co II redox signals of receptor 3 and 4 disappear gradually when the fluoride or acetate anions are added. Moreover, visual color changes accompany guest binding, enabling this system to act as colorimetric anion sensors. The colorimetric properties of these sensors are ascribed to the hydrogen-bond formation and the colorimetric group quinoxaline. The Royal Society of Chemistry 2009.

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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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Cl- and H2PO4- anion selectivity properties of new heteroditopic RuII and ReI bipyridyl bis(benzo-15-crown-5) receptors are remarkably dependent upon the presence of co-bound intramolecular sandwich crown ether complexed K+.

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

The reaction rate of a catalyzed reaction is faster than the reaction rate of the uncatalyzed reaction at the same temperature.15746-57-3, Name is Cis-Dichlorobis(2,2′-bipyridine)ruthenium(II), molecular formula is C20H16Cl2N4Ru. In a Article，once mentioned of 15746-57-3, HPLC of Formula: C20H16Cl2N4Ru

We present the postmodification of a diamondoid 3D supramolecular organic framework (SOF) to append [Ru(BPY)3]2+ groups through the formation of a hydrazone bond. The resulting SOF works as an efficient recyclable heterogeneous catalyst for visible-light-induced reduction of aromatic azides to amines.

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