Synthèse et propriétés de diodes électroniquement couplées composées d'une porphyrine de zinc et d'une porphyrine d'or pour la séparation de charges

Communication par affiche intitulée (présentée par J. Fortage) : Synthèse et propriétés de diodes électroniquement couplées composées d'une porphyrine de zinc et d'une porphyrine d'or pour la séparation de charge

Cadmium-free CuInS 2 /ZnS quantum dots as efficient and robust photosensitizers in combination with a molecular catalyst for visible light-driven H 2 production in water

International audienc

Cadmium-free CuInS 2 /ZnS quantum dots as efficient and robust photosensitizers in combination with a molecular catalyst for visible light-driven H 2 production in water

International audienc

Cadmium-free CuInS 2 /ZnS quantum dots as efficient and robust photosensitizers in combination with a molecular catalyst for visible light-driven H 2 production in water

International audienc

Cobalt(III) tetraaza-macrocyclic complexes as efficient catalyst for photoinduced hydrogen production in water: Theoretical investigation of the electronic structure of the reduced species and mechanistic insight

We recently reported a very efficient homogeneous system for visible-light driven hydrogen production in water based on the cobalt(III) tetraaza-macrocyclic complex [Co(CR)Cl2]+ (1) (CR = 2,12-dimethyl-3,7,11,17-tetra-azabicyclo(11.3.1)-heptadeca-1(17),2,11,13,15-pentaene) as a noble metal-free catalyst, with [RuII(bpy)3]2+ (Ru) as photosensitizer and ascorbate/ascorbic acid (HA-/H2A) as a sacrificial electron donor and buffer (PhysChemChemPhys 2013, 15, 17544). This catalyst presents the particularity to achieve very high turnover numbers (TONs) (up to 1000) at pH 4.0 at a relative high concentration (0.1 mM) generating a large amount of hydrogen and having a long term stability. A similar activity was observed for the aquo derivative [CoIII(CR)(H2O)2]3+ (2) due to substitution of chloro ligands by water molecule in water. In this work, the geometry and electronic structures of 2 and its analog [ZnII(CR)Cl]+ (3) derivative containing the redox innocent Zn(II) metal ion have been investigated by DFT calculations under various oxidation states. We also further studied the photocatalytic activity of this system and evaluated the influence of varying the relative concentration of the different components on the H2-evolving activity. Turnover numbers versus catalyst (TONCat) were found to be dependent on the catalyst concentration with the highest value of 1130 obtained at 0.05 mM. Interestingly, the analogous nickel derivative, [NiII(CR)Cl2] (4), when tested under the same experimental conditions was found to be fully inactive for H2 production. Nanosecond transient absorption spectroscopy measurements have revealed that the first electron-transfer steps of the photocatalytic H2-evolution mechanism with the Ru/cobalt tetraaza/HA-/H2A system involve a reductive quenching of the excited state of the photosensitizer by ascorbate (kq = 2.5 × 107 M-1 s-1) followed by an electron transfer from the reduced photosensitizer to the catalyst (ket = 1.4 × 109 M-1 s-1). The reduced catalyst can then enter into the cycle of hydrogen evolution

Synthesis, structure, spectroscopy and reactivity of new heterotrinuclear water oxidation catalysts

Four heterotrinuclear complexes containing the ligands 3,5-bis(2-pyridyl)pyrazolate (bpp−) and 2,2′:6′,2′′-terpyridine (trpy) of the general formula {[RuII(trpy)]2(μ-[M(X)2(bpp)2])}(PF6)2, where M = CoII, MnII and X = Cl−, AcO− (M = CoII, X = Cl−: Ru2Co–Cl2; M = MnII, X = Cl−: Ru2Mn–Cl2; M = CoII, X = AcO−: Ru2Co–OAc2; M = MnII, X = AcO−: Ru2Mn–OAc2), have been prepared for the first time. The complexes have been characterized using different spectroscopic techniques such as UV-vis, IR, and mass spectrometry. X-Ray diffraction analyses have been used to characterize the Ru2Mn–Cl2 and Ru2Mn–OAc2 complexes. The cyclic voltammograms (CV) for all four complexes in organic solvent (CH3CN or CH2Cl2) display three successive reversible oxidative waves corresponding to one-electron oxidations of each of the three metal centers. The oxidized forms of the complexes Ru2Co–OAc2 and Ru2Mn–OAc2 are further characterized by EPR and UV-vis spectroscopy. The magnetic susceptibility measurements of all complexes in the temperature range of 2–300 K reveal paramagnetic properties due to the presence of high spin Co(II) and Mn(II) centers. The complexes Ru2Co–OAc2 and Ru2Mn–OAc2 act as precatalysts for the water oxidation reaction, since the acetato groups are easily replaced by water at pH = 7 generating the active catalysts, {[Ru(H2O)(trpy)]2(μ-[M(H2O)2(bpp)2])}4+ (M = CoII: Ru2Co–(H2O)4; M = MnII: Ru2Mn–(H2O)4). The photochemical water oxidation reaction is studied using [Ru(bpy)3]2+ as the photosensitizer and Na2S2O8 as a sacrificial electron acceptor at pH = 7. The Co containing complex generates a TON of 50 in about 10 minutes (TOFi = 0.21 s−1), whereas the Mn containing complex only generates a TON of 8. The water oxidation reaction of Ru2Co–(H2O)4 is further investigated using oxone as a sacrificial chemical oxidant at pH = 7. Labelled water oxidation experiments suggest that a nucleophilic attack mechanism is occurring at the Co site of the trinuclear complex with cooperative involvement of the two Ru sites, via electronic coupling through the bpp− bridging ligand and via neighboring hydrogen bonding

[Rh^III(dmbpy)₂Cl₂]⁺ as a highly efficient catalyst for visible-light-driven hydrogen production in pure water: comparison with other rhodium catalysts

We report a very efficient homogeneous system for the visible-light-driven hydrogen production in pure aqueous solution at room temperature. This comprises [RhIII(dmbpy)2Cl2]Cl (1) as catalyst, [Ru(bpy)3]Cl2 (PS1) as photosensitizer, and ascorbate as sacrificial electron donor. Comparative studies in aqueous solutions also performed with other known rhodium catalysts, or with an iridium photosensitizer, show that 1) the PS1/1/ascorbate/ascorbic acid system is by far the most active rhodium-based homogeneous photocatalytic system for hydrogen production in a purely aqueous medium when compared to the previously reported rhodium catalysts, Na3[RhI(dpm)3Cl] and [RhIII(bpy)Cp*(H2O)]SO4 and 2) the system is less efficient when [IrIII(ppy)2(bpy)]Cl (PS2) is used as photosensitizer. Because catalyst 1 is the most efficient rhodium-based H2-evolving catalyst in water, the performance limits of this complex were further investigated by varying the PS1/1 ratio at pH 4.0. Under optimal conditions, the system gives up to 1010 turnovers versus the catalyst with an initial turnover frequency as high as 857 TON h−1. Nanosecond transient absorption spectroscopy measurements show that the initial step of the photocatalytic H2-evolution mechanism is a reductive quenching of the PS1 excited state by ascorbate, leading to the reduced form of PS1, which is then able to reduce [RhIII(dmbpy)2Cl2]+ to [RhI(dmbpy)2]+. This reduced species can react with protons to yield the hydride [RhIII(H)(dmbpy)2(H2O)]2+, which is the key intermediate for the H2 production

Synthesis, characterization, and photocatalytic H₂-evolving activity of a family of [Co(N4Py)(X)]^<i>n</i>+ complexes in aqueous solution

International audienceA series of [CoIII(N4Py)(X)](ClO4)n (X = Cl-, Br-, OH-, N3 -, NCS--κN, n = 2: X = OH2, NCMe, DMSO-κO, n = 3) complexes containing the tetrapyridyl N5 ligand N4Py (N4Py = 1,1-di(pyridin-2-yl)-N,N-bis(pyridin-2-ylmethyl)methanamine) has been prepared and fully characterized by infrared (IR), UV-visible, and NMR spectroscopies, high-resolution electrospray ionization mass spectrometry (HRESI-MS), elemental analysis, X-ray crystallography, and electrochemistry. The reduced Co(II) and Co(I) species of these complexes have been also generated by bulk electrolyses in MeCN and characterized by UV-visible and EPR spectroscopies. All tested complexes are catalysts for the photocatalytic production of H2 from water at pH 4.0 in the presence of ascorbic acid/ascorbate, using [Ru(bpy)3]2+ as a photosensitizer, and all display similar H2-evolving activities. Detailed mechanistic studies show that while the complexes retain the monodentate X ligand upon electrochemical reduction to Co(II) species in MeCN solution, in aqueous solution, upon reduction by ascorbate (photocatalytic conditions), [CoII(N4Py)(HA)]+ is formed in all cases and is the precursor to the Co(I) species which presumably reacts with a proton. These results are in accordance with the fact that the H2-evolving activity does not depend on the chemical nature of the monodentate ligand and differ from those previously reported for similar complexes. The catalytic activity of this series of complexes in terms of turnover number versus catalyst (TONCat) was also found to be dependent on the catalyst concentration, with the highest value of 230 TONCat at 5 × 10-6 M. As revealed by nanosecond transient absorption spectroscopy measurements, the first electron-transfer steps of the photocatalytic mechanism involve a reductive quenching of the excited state of [Ru(bpy)3]2+ by ascorbate followed by an electron transfer from [RuII(bpy)2(bpy•-)]+ to the [CoII(N4Py)(HA)]+ catalyst. The reduced catalyst then enters into the H2-evolution cycle