Search results for "Electron transfer"
showing 10 items of 282 documents
Intramolecular electron transfer between molybdenum and iron mimicking bacterial sulphite dehydrogenase
2014
Diferrocenyl/diferrocenium substituted dioxido molybdenum(VI) complexes [Fe2MoO2] 2(Fc)/[2(FC)]²⁺ mimic the catalytic active site including the redox subunits as well as the catalytic function of bacterial sulphite oxidases.
The oxidation of ubiquinol by the isolated rieske iron-sulfur protein in solution
1990
The pre-steady-state redox reactions of the Rieske iron-sulfur protein isolated from beef heart mitochondria have been characterized. The rates of oxidation by c-type cytochromes is much faster than the rate of reduction by ubiquinols. This enables the monitoring of the oxidation of ubiquinols by the Rieske protein through the steady-state electron transfer to cytochrome c in solution. The pH and ionic strength dependence of this reaction indicate that the ubiquinol anion is the direct reductant of the oxidized cluster of the iron-sulfur protein. The second electron from ubiquinol is diverted to oxygen by the isolated Rieske protein, and forms oxygen radicals that contribute to the steady-s…
Stereodifferentiation in the formation and decay of the encounter complex in bimolecular electron transfer with photoactivated acceptors.
2005
Experimental evidence has been obtained for the involvement of encounter complexes between both enantiomers of a π,π* triplet excited ketone and a chiral phenol or indole. Determination of the pre-equilibrium constants (KEC) and the intrinsic decay rate constants (kd) indicates a significant stereodifferentiation in both steps of the quenching process. Perez Prieto, Julia, Julia.Perez@uv.es ; Galian, Raquel Eugenia, Raquel.Galian@uv.es ; Morant Miñana, Maria Carmen, Maica.Morant@uv.es
Electron-Transfer Kinetics for Generation of Organoiron(IV) Porphyrins and the Iron(IV) Porphyrin π Radical Cations
1999
Homogeneous electron-transfer kinetics for the oxidation of seven different iron(III) porphyrins using three different oxidants were examined in deaerated acetonitrile, and the resulting data were evaluated in light of the Marcus theory of electron transfer to determine reorganization energies of the rate-determining oxidation of iron(III) to iron(IV). The investigated compounds are represented as (P)Fe(R), where P = the dianion of 2,3,7,8,12,13,17,18-octaethyl-5,10,15,20-tetraphenylporphyrin (OETPP) and R = C6H5, 3,5-C6F2H3, 2,4,6-C6F3H2, or C6F5 or P = the dianion of 2,3,7,8,12,13,17,18-octaethylporphyrin (OEP) and R = C6H5, 2,4,6-C6F3H2, or 2,3,5,6-C6F4H. The first one-electron transfer …
Photocatalytic activity of nano and microcrystalline TiO2 hybrid systems involving phthalocyanine or porphyrin sensitizers
2011
Hybrid photocatalysts based on TiO(2)-anatase matrix, representing the both micro- and nano-structures, impregnated with selected lanthanide diphthalocyanine and metalloporphyrin sensitizers, were compared to evaluate their activity and effectiveness in a water suspension catalytic system designed to degrade 4-nitrophenol (4-NP) in a UV-stimulated reaction. Either type of the anatase catalyst was proved to be effective in mineralizing of 4-NP. However, kinetic studies confirmed that the composite's efficiency basically depends on the nature of the macromolecular sensitizer and to a minor extent on the dimensions (micro/nano) of the TiO(2) particles. The apparent higher activity observed for…
Chemisorption of Atomically Precise 42-Carbon Graphene Quantum Dots on Metal Oxide Films Greatly Accelerates Interfacial Electron Transfer
2019
Graphene quantum dots (GQDs) are emerging as environmentally friendly, low-cost, and highly tunable building blocks in solar energy conversion architectures, such as solar (fuel) cells. Specifically, GQDs constitute a promising alternative for organometallic dyes in sensitized oxide systems. Current sensitized solar cells employing atomically precise GQDs are based on physisorbed sensitizers, with typically limited efficiencies. Chemisorption has been pointed out as a solution to boost photoconversion efficiencies, by allowing improved control over sensitizer surface coverage and sensitizer-oxide coupling strength. Here, employing time-resolved THz spectroscopy, we demonstrate that chemisor…
Light-induced decarboxylation in a photo-responsive iron-containing complex based on polyoxometalate and oxalato ligands.
2016
A new iron-oxalato polyoxometalate exhibits a remarkable photocoloration effect in the solid state based entirely on an intramolecular process.
Alcohol oxidation by dioxygen and aldehydes catalysed by square-planar cobalt(III) complexes of disubstituted oxamides and related ligands
2001
The square-planar cobalt(III) complexes of o-phenylenebis(N′-methyloxamidate) (Me2opba) and related oxamate (Meopba) and bis(oxamate) (opba) ligands catalyse the selective oxidation, by dioxygen and pivalaldehyde, of a wide range of secondary alcohols to the corresponding ketones, in good yields and under mild conditions in acetonitrile at room temperature. Thus, the oxidation of the series of α-alkylbenzyl alcohols PhCH(OH)R (R = Me, Et, iPr, tBu) results in the exclusive formation of ketones as a product of C−H bond cleavage, and no C−C bond cleavage products are observed in any case. The modulation of catalytic activity by ligand substituents among this series of cobalt catalysts highlig…
Luminescence and Light‐Driven Energy and Electron Transfer from an Exceptionally Long‐Lived Excited State of a Non‐Innocent Chromium(III) Complex
2019
Abstract Photoactive metal complexes employing Earth‐abundant metal ions are a key to sustainable photophysical and photochemical applications. We exploit the effects of an inversion center and ligand non‐innocence to tune the luminescence and photochemistry of the excited state of the [CrN6] chromophore [Cr(tpe)2]3+ with close to octahedral symmetry (tpe=1,1,1‐tris(pyrid‐2‐yl)ethane). [Cr(tpe)2]3+ exhibits the longest luminescence lifetime (τ=4500 μs) reported up to date for a molecular polypyridyl chromium(III) complex together with a very high luminescence quantum yield of Φ=8.2 % at room temperature in fluid solution. Furthermore, the tpe ligands in [Cr(tpe)2]3+ are redox non‐innocent, …
Zn(II)-coordination and fluorescence studies of a new polyazamacrocycle incorporating 1H-pyrazole and naphthalene units.
2010
The synthesis and Zn(2+) coordination properties of a new macrocycle (L1) obtained by dipodal (2 + 2) condensation of the polyamine 3-(naphthalen-2-ylmethyl)pentane-1,5-diamine with 1H-pyrazole-3,5-dicarbaldehyde are reported. pH-metric studies show that L1 bears five measurable protonation steps in the 2.0-11.0 pH range. Fluorescence emission studies indicate that the removal of the first proton from the H(5)L1(5+) species leads to a significant decrease in the emission due to a photoinduced electron transfer process. Addition of Zn(2+) promotes a boat-like conformation that approaches both fluorophores and facilitates the formation of an excimer which reaches its highest emission for a 1 …