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TTF-annulated phenanthroline and unexpected oxidative cleavage of the C=C bond in its ruthenium(II) complex

Tetrathiafulvalene (TTF) and 1, 10-phenanthroline have been fused together via a simple and efficient synthetic procedure that provides a new bidentate ligand, 40, 50-ethylenedithiotetrathiafulvenyl[4, 5-f]-[1, 10]phenanthroline (EDT-TTF-phen, 1). Its ruthenium(II) complex exhibits a unique packing of TTF subunits in the solid state. In an acetonitrile solution, [Ru(bpy) 2(1)](PF6)2 undergoes facile oxidative cleavage of the C=C double bond, which cannot be observed in the dark or under anaerobic conditions. This points to the photocatalytic role played by the ruthenium(II) chromophore in this conversion.

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

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Intramolecular electronic energy transfer in ruthenium(II) diimine donor/pyrene acceptor complexes linked by a single C-C bond

The photophysical behavior of [(bpy)2Ru(L)]2+ complexes L = 4-(1′-pyrenyl)-2,2′-bipyridine, bpy-pyr; 2-(1′–pyrenyl)-1,10-phenanthroline, phen-pyr; and 2-(2′-naphthyl)-1,10-phenanthroline, phen-nap) was investigated in solutions and frozen matrices. The conformation of the linked pyrene differs in the two complexes: The pyrene moiety is conformationally constrained to be nearly perpendicular to the phenanthroline in the phen-pyr complex while the pyrene in the bpy-pyr complex has much greater flexibility about the C-C bond linking the ligand and the pyrene. The 3MLCT excited state of the Ru(II) diimine complex and the 3 (pi?pi*) state of the pyrenyl substituent are nearly isoenergetic; the 3MLCT state is the lowest energy state in the bpy-pyr complex, and the pyrene 3(pi?pi*) state is lower in energy for the phen-pyr complex. The bpy-pyr complex is unique in that the3MLCT state has a very long lived luminescence (approximately 50 mus in degassed CH3CN). Luminescence decays for both pyrene containing complexes can be fit as double exponentials, indicating that the 3MLCT and 3(pi?pi*) states are not in equilibrium. Analysis of decays obtained at several temperatures reveal that energy transfer is slower than relaxation of the 3MLCT state but more rapid than decay of the pyrene localized3(pi?pi*) state. The results also suggest that electronic coupling between the two states is weak despite the fact that the two chromophores are separated by a single covalent bond.

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

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Intramolecular Electron-Transfer of Covalently-Linked Polypyridine Ruthenium(II)Rhodium(III) Binuclear Complexes in the Excited State. Observation of the Marcus Inverted Region

Ru(II)bpy2Mebpy-CH2CH(OH)CH2-MebpyRh(III)L2 (L=bpy.phen) (1) were newly synthesized.Intramolecular electron-transfer in excited 1 was studied with a time-correlated single photon counting method.In H2O, the excited Ru(II) complex exhibits a biexponential decay.The presence of a slow component suggests that the excited state can be repopulated by thermal activation from the (Ru(III)-Rh(II) and the direct process to the ground state lies in the Marcus Inverted region.

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

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Ruthenium(ll) complexes incorporating 2-(2?-Pyridyl)pyrimidine-4- carboxylic acid

A new bidentate ligand bearing a single carboxylate functionality, 2-(2?-pyridyl)pyrimidine-4-carboxylic acid (cppH), has been prepared and applied in the synthesis of a series of ruthenium(ll) complexes. Reaction of this new ligand with RuII(bpy)2CI2 led to the unexpected oxidation of the starting material to give [RuIII(bpy) 2CI2]CI ¡¤ H2O and a low yield of [RuII(bpy)2(cppH)](PF6)2 ¡¤ H2O (1) on addition of an aqueous KPF6 solution (bpy = 2,2?-bipyridine and cpp = 4-carboxylate-2?-pyridyl-2-pyrimidine). An X-ray crystal structure determination on crystals of 1a, [Ru II(bpy)2(cpp)](PF6), obtained from slow evaporation of an aqueous solution of 1 revealed that the nitrogen para to the carboxylate group in the cpp- ligand coordinates to the ruthenium(ll) center rather than that ortho to this group. The same complex was prepared via decarbonylation of [RuII(cppH)(CO)2CI2] ¡¤ H2O in the presence of bpy and an excess of trimethylamine-N-oxide (Me3NO), as the decarbonylation agent. The coordination of cppH in the precursor is the same as in the final product. The related complex [RuII(phen)2(cppH)](PF6) 2 ¡¤ 2H2O (2) (phen = 1,10-phenanthroline) was similarly synthesized. [RuII(bpy)(dppz)(cppH)](PF6) 2 ¡¤ CH3CN (3) (dppz = dipyrido[3,2,- a;2?,3-c]phenazine) was also prepared by photochemical decarbonylation of [RuII(bpy)(CO)2CI2] giving [Ru II(bpy)- (CO)CI2]2 followed by bridge splitting with dppz to generate [RuII(bpy)(dppz)(CO)CI](PF6) ¡¤ H2O. This intermediate was then reacted with cppH to produce 3, as a mixture of geometric isomers. In contrast to 1, X-ray crystallography on the major product isolated from this mixture, [RuII(bpy)(dppz) (cpp)](NO3) ¡¤ 10H2O, 3N3 indicated that the nitrogen adjacent to the carboxylate was coordinated to ruthenium(ll). Full characterization of these complexes has been undertaken including the measurement of UV-visible and emission spectra. Electrochemical and spectroelectro-chemical studies in acetonitrile show that these complexes undergo reversible oxidation from RuII to RuIII at potentials of 983 ¡À 3 mV, 1004 ¡À 5 mV, and 1023 ¡À 3 mV versus Fc0/+ (Fc = Ferrocene) for 1, 2, and 3N3, respectively.

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

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Hole tunneling and hopping in a Ru(bpy)32+- phenothiazine dyad with a bridge derived from oligo-p-phenylene

A molecular dyad was synthesized in which a Ru(bpy)3 2+ (bpy = 2,2?-bipyridine) photosensitizer and a phenothiazine redox partner are bridged by a sequence of tetramethoxybenzene, p-dimethoxybenzene, and p-xylene units. Hole transfer from the oxidized metal complex to the phenothiazine was triggered using a flash-quench technique and investigated by transient absorption spectroscopy. Optical spectroscopic and electrochemical experiments performed on a suitable reference molecule in addition to the above-mentioned dyad lead to the conclusion that hole transfer from Ru(bpy)33+ to phenothiazine proceeds through a sequence of hopping and tunneling steps: Initial hole hopping from Ru(bpy) 33+ to the easily oxidizable tetramethoxybenzene unit is followed by tunneling through the barrier imposed by the p-dimethoxybenzene and p-xylene spacers. The overall charge transfer proceeds with a time constant of 41 ns, which compares favorably to a time constant of 1835 ns associated with equidistant hole tunneling between the same donor-acceptor couple bridged by three identical p-xylene units. The combined hopping/tunneling sequence thus leads to an acceleration of hole transfer by roughly a factor of 50 when compared to a pure tunneling mechanism.

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

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Synthesis and excited-state propertdies of a novel ruthenium nucleoside: 5-[Ru(bpy)2(4-m-4?-pa-bpy)]2+-2?-deoxyuridine

The synthesis and photophysical properties of a novel ruthenium-modified nucleoside are reported. The key synthetic step to 5-[Ru(bpy)2(4-m-4?-pa-bpy)]2+-2?-deoxyuridine involves the Pd(0)-catalyzed cross-coupling of a propargylamine-derivatized Ru(bpy)32+ and 3?,5?-dibenzoyloxy-2?-deoxy-5-iodouridine. The long-lived 3MLCT excited state (1300 ns) of 5-[Ru(bpy)2(4-m-4?-pa-bpy)]2+-2?-deoxyuridine has an emission maximum centered at 640 nm. Step-scan Fourier transform infrared (S2FTIR) time-resolved spectroscopy reveals the excited-state electron to be localized on the modified bipyridine with the excited-state dipole oriented toward the 2?-deoxyuridine.

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

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Interfacial energy conversion in RuII polypyridyl-derivatized oligoproline assemblies on TiO2

Solid-phase peptide synthesis has been applied to the preparation of phosphonate-derivatized oligoproline assemblies containing two different Ru II polypyridyl chromophores coupled via “click” chemistry. In water or methanol the assembly adopts the polyproline II (PPII) helical structure, which brings the chromophores into close contact. Excitation of the assembly on ZrO2 at the outer RuII in 0.1 M HClO 4 at 25 C is followed by rapid, efficient intra-assembly energy transfer to the inner RuII (kEnT = 3.0 ¡Á 10 7 s-1, implying 96% relative efficiency). The comparable energy transfer rate constants in solution and on nanocrystalline ZrO 2 suggest that the PPII structure is retained when bound to ZrO 2. On nanocrystalline films of TiO2, excitation at the inner RuII is followed by rapid, efficient injection into TiO 2. Excitation of the outer RuII is followed by rapid intra-assembly energy transfer and then by electron injection. The oligoproline/click chemistry approach holds great promise for the preparation of interfacial assemblies for energy conversion based on a family of assemblies having controlled compositions and distances between key functional groups.

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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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Visible light-mediated oxidative quenching reaction to electron-rich epoxides: Highly regioselective synthesis of alpha-bromo (di)ketones and mechanism study

A novel and simple procedure was developed for the regioselective synthesis of alpha-bromo (di)ketones from electron-rich epoxides via visible light photoredox catalysis. Through optimization of solvent and light source, the reaction can be rapidly achieved under mild conditions. Moreover, the possible reaction mechanism was proposed and further supported by control experiments.

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

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Synthesis and characterisation of bis(2,2?-bipyridine)(4-carboxy-4?-(pyrid-2-ylmethylamido)-2,2?-bipyridine)ruthenium(II) di(hexafluorophosphate): Comparison of spectroelectrochemical properties with related complexes

The new complex, [RuII(bpy)2(4-HCOO-4?-pyCH2 NHCO-bpy)](PF6)2 ¡¤ 3H2O (1), where 4-HCOO-4?-pyCH2NHCO-bpy is 4-(carboxylic acid)-4?-pyrid-2-ylmethylamido-2,2?-bipyridine, has been synthesised from [Ru(bpy)2(H2dcbpy)](PF6)2 (H2dcbpy is 4,4?-(dicarboxylic acid)-2,2?-bipyridine) and characterised by elemental analysis and spectroscopic methods. An X-ray crystal structure determination of the trihydrate of the [Ru(bpy)2(H2dcbpy)](PF6)2 precursor is reported, since it represented a different solvate to an existing structure. The structure shows a distorted octahedral arrangement of the ligands around the ruthenium(II) centre and is consistent with the carboxyl groups being protonated. A comparative study of the electrochemical and photophysical properties of [RuII(bpy)2(4-HCOO-4?-pyCH2NHCO-bpy)]2+ (1), [Ru(bpy)2(H2dcbpy)]2+ (2), [Ru(bpy)3]2+ (3), [Ru(bpy)2Cl2] (4) and [Ru(bpy)2Cl2]+ (5) was then undertaken to determine their variation upon changing the ligands occupying two of the six ruthenium(II) coordination sites. The ruthenium(II) complexes exhibit intense ligand centred (LC) transition bands in the UV region, and broad MLCT bands in the visible region. The ruthenium(III) complex, 5, displayed overlapping LC bands in the UV region and a LMCT band in the visible. 1, 2 and 3 were found, via cyclic voltammetry at a glassy carbon electrode, to exhibit very positive reversible formal potentials of 996, 992 and 893 mV (versus Fc/Fc+) respectively for the Ru(III)/Ru(II) half-cell reaction. As expected the reversible potential derived from oxidation of 4 (-77 mV (versus Fc/Fc+)) was in excellent agreement with that found via reduction of 5 (-84 mV (versus Fc/Fc+)). Spectroelectrochemical experiments in an optically transparent thin-layer electrochemical cell configuration allowed UV-Vis spectra of the Ru(III) redox state to be obtained for 1, 2, 3 and 4 and also confirmed that 5 was the product of oxidative bulk electrolysis of 4. These spectrochemical measurements also confirmed that the oxidation of all Ru(II) complexes and reduction of the corresponding Ru(III) complex are fully reversible in both the chemical and electrochemical senses. Crown Copyright

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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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Unusual photophysical properties of a ruthenium(II) complex related to [Ru(bpy)2(dppz)]2+

A new ruthenium polypyridyl complex, [Ru(bpy)2(dpqp)] 2+ (bpy = 2,2?-bipyridne; dpqp = pyrazino[2?,3?:5, 6]pyrazino[2,3-f][1,10]phenanthroline), shows strong luminescence in water at room temperature, a behavior that is strikingly different from that of the nonemissive “DNA light-switch” prototype [Ru(bpy)2(dppz)] 2+ (dppz = dipyrido[3,2-a:2?-3?-c]phenazine) under similar conditions. Variation of the absorption and emission spectra of [Ru(bpy)2(dpqp)]2+ as a function of the pH is consistent with the occurrence of two ground-state protonation steps associated with the dpqp ligand and an apparent pKa* of 2.1. Electrochemistry and theoretical calculations indicate that the lowest unoccupied molecular orbital (LUMO) of [Ru(bpy)2(dpqp)]2+ is localized on the distal portion of the dpqp ligand and lies at a lower energy than the dppz-based LUMO of [Ru(bpy)2(dppz)]2+. The combination of its strong DNA binding affinity and relatively long-lived triplet metal-to-ligand charge-transfer excited state in an aqueous solution results in more efficient DNA photocleavage by [Ru(bpy)2(dpqp)]2+ than [Ru(bpy) 2(dppz)]2+.

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