A5039702991- X-ray Diffraction in Crystallography
- Crystallization and Solubility Studies
- Metal complexes synthesis and properties
- Metalloenzymes and iron-sulfur proteins
- Magnetism in coordination complexes
- Crystallography and molecular interactions
- Electrocatalysts for Energy Conversion
- Metal-Catalyzed Oxygenation Mechanisms
- CO2 Reduction Techniques and Catalysts
- Metal-Organic Frameworks: Synthesis and Applications
- Advanced Photocatalysis Techniques
- Lanthanide and Transition Metal Complexes
- Advanced battery technologies research
- Electrochemical Analysis and Applications
- Organometallic Complex Synthesis and Catalysis
- Ammonia Synthesis and Nitrogen Reduction
- Polyoxometalates: Synthesis and Applications
- Porphyrin and Phthalocyanine Chemistry
- Electrochemical sensors and biosensors
- X-ray Spectroscopy and Fluorescence Analysis
- Electron Spin Resonance Studies
- Trace Elements in Health
- Vanadium and Halogenation Chemistry
- Catalysis for Biomass Conversion
- Covalent Organic Framework Applications
Département de Chimie Moléculaire
2016-2025
Centre National de la Recherche Scientifique
2015-2024
Université Grenoble Alpes
2015-2024
Universidad Autónoma de Madrid
2013-2015
Université Joseph Fourier
2010-2014
Institut de Chimie Moléculaire de Grenoble
2011-2014
Laboratoire de Chimie
2011-2014
University of Parma
2004-2012
Abstract The development of multicomponent molecular systems for the photocatalytic reduction water to hydrogen has experienced considerable growth since end 1970s. Recently, with aim improving efficiency catalysis, single‐component photocatalysts have been developed in which photosensitizer is chemically coupled hydrogen‐evolving catalyst same molecule through a bridging ligand. Until now, none these operated efficiently pure aqueous solution: highly desirable medium energy‐conversion...
Three new cyclometalated iridium complexes were prepared and investigated on nanocrystalline NiO cathodes. Nanosecond transient absorption spectroscopy experiments show they present a surprisingly slow geminate charge recombination upon excitation NiO, representing thus the first examples of simple sensitizers with such feature. These used in dye-sensitized solar cells using film as semiconductor. The long-lived separated state these Ir make them compatible other redox mediators than...
In the oxygen reduction reaction (ORR) domain, investigation of new homogeneous catalysts is a crucial step toward full comprehension key structural and/or electronic factors that control catalytic efficiency and selectivity. Herein, we report unique non-heme diiron complex can act as ORR catalyst in acetonitrile solution. This iron(II) thiolate dinuclear complex, [FeII2(LS)(LSH)] ([Fe2SH]+) (LS2– = 2,2′-(2,2′-bipyridine-6,6′-diyl)bis(1,1-diphenylethanethiolate)) contains thiol group metal...
Herein, we describe an uncommon example of a manganese–thiolate complex, which is capable activating dioxygen and catalyzing its two-electron reduction to generate H2O2. The structurally characterized dimercapto-bridged MnII dimer [MnII2(LS)(LSH)]ClO4 (MnII2SH) formed by reaction the LS ligand (2,2′-(2,2′-bipyridine-6,6′-diyl)bis(1,1-diphenylethanethiolate)) with MnII. unusual presence pendant thiol group bound one ion in MnII2SH evidenced both solid state solution. complex reacts CH3CN,...
ConspectusSulfur-rich metalloproteins and metalloenzymes, containing strongly covalent metal–thiolate (cysteinate) or metal–sulfide bonds in their active site, are ubiquitous nature. The metal–sulfur motif is a highly versatile tool involved various biological processes: (i) metal storage, transport, detoxification; (ii) electron transfer; (iii) activation of the sulfur atom to promote different types S-based reactions including S-alkylation, S-oxygenation, S-nitrosylation, disulfide thiyl...
Abstract We report a very efficient homogeneous system for the visible‐light‐driven hydrogen production in pure aqueous solution at room temperature. This comprises [Rh III (dmbpy) 2 Cl ]Cl ( 1 ) as catalyst, [Ru(bpy) 3 PS1 photosensitizer, and ascorbate sacrificial electron donor. Comparative studies solutions also performed with other known rhodium catalysts, or an iridium show that 1) / /ascorbate/ascorbic acid is by far most active rhodium‐based photocatalytic purely medium when compared...
Despite the report of several structural and functional models [NiFe]-hydrogenases, it is still unclear how succession electron proton transfers during H2 production catalysis are controlled in terms both sequence (order chemical or redox steps) sites (metal and/or ligand). To address this issue, structure previously described bioinspired [NiFe]-hydrogenase complex [LN2S2NiIIFeIICp(CO)]+ (LNiIIFeIICp, with LN2S2 = 2,2′-(2,2′-bipyridine-6,6′-diyl)bis(1,1′-diphenylethanethiolate) Cp...
[NiFe]-hydrogenase enzymes are efficient catalysts for H2 evolution but their synthetic models have not been reported to be active under aqueous conditions so far. Here we show that a close model of the site can work as very and stable heterogeneous catalyst mildly acidic conditions. Entry in catalysis is NiI FeII complex, with electronic structure analogous Ni-L state enzyme, corroborating mechanism modification recently proposed [NiFe]-hydrogenases.
The complexation of a preorganized thioether-functionalized bis(pyrazolyl)methane ligand (L) with silver precursors produces supramolecular structures organized at two hierarchical levels: [AgL](6)(X)(6) metal-organic cyclic hexamers and their organization in 3D architectures. toroidal 22-26 Å external diameter are found to be stable already solution before self-assembly into the crystalline state. In lattice, hexameric building block arranged different highly symmetric space groups as...
A {Cu2S2} diamond core has been stabilized thanks to the synthesis of a novel dinucleating ligand. The resulting dicopper complex isolated in two formal oxidation states (see picture) that mimic most essential structural, spectroscopic, and functional properties CuA center. Detailed facts importance specialist readers are published as "Supporting Information". Such documents peer-reviewed, but not copy-edited or typeset. They made available submitted by authors. Please note: publisher is...
The photoelectrochemical activity of a mesoporous NiO electrode sensitized by ruthenium complex was investigated with several rhodium and cobalt H2-evolving catalysts. Photocurrent as high 80 μA/cm2 produced irradiation such photocathode in the presence Rh(III) polypyridyl complexes, while complexes gave almost no photocurrent. Photolysis experiments led to two-electron reduced form into Rh(I) demonstrate occurrence an electron transfer chain from catalyst. Mott–Schottky evidenced pH...
Herein, Ca K-edge X-ray absorption spectroscopy (XAS) is developed as a means to characterize the local environment of calcium centers. The spectra for six, seven, and eight coordinate inorganic molecular complexes were analyzed determined be primarily influenced by coordination site symmetry at center. experimental results are closely correlated time-dependent density functional theory (TD-DFT) calculations XAS spectra. applicability this methodology complex systems was investigated using...
Abstract Disulfide/thiolate interconversion supported by transition‐metal ions is proposed to be implicated in fundamental biological processes, such as the transport of metal or regulation production reactive oxygen species. We report herein a mononuclear dithiolate Co III complex, [Co LS(Cl)] ( 1 ; LS=sulfur containing ligand), that undergoes clean, fast, quantitative and reversible II disulfide/Co thiolate mediated chloride anion. The removal Cl − from complex leads formation...
A bisamine aliphatic dithiolate [NiIIN2S2] complex that does yield a metal-based oxidation has been synthesized. square pyramidal [NiIIIN3S2]+ is generated by electrochemical in the presence of imidazole, mimicking redox structural changes NiSOD. In addition, EPR measurements coupled to DFT calculations demonstrate metal character active orbital increases drastically upon imidazole binding, implicating these geometrical modifications are crucial for stabilization NiIII state.
Sulfur-rich nickel metalloenzymes are capable of stabilizing NiI and NiIII oxidation states in catalytically relevant species. In an effort to better understand the structural electronic features that allow stabilization such species, we have investigated electrochemical properties two mononuclear N2S2 NiII complexes differ their sulfur environment. Complex 1 aliphatic dithiolate coordination ([NiL], 1), complex 2I is characterized by mixed thiolate/thioether ([NiLMe]I, 2I). The latter...
This study deals with the unprecedented reactivity of dinuclear non-heme Mn
In the quest for new, efficient, and noble-metal-free H2-evolution catalysts, hydrogenase enzymes are a source of inspiration. Here, we describe development new hybrid material based on structural functional [NiFe]-hydrogenase model complex (NiFe) incorporated into Zr-based MOF PCN-777. The bulk NiFe@PCN-777 was synthesized by simple encapsulation. Characterization solid-state NMR IR spectroscopy, SEM-EDX, ICP-OES, gas adsorption confirmed inclusion guest. FTO-supported thin films composite...
Abstract The development of multicomponent molecular systems for the photocatalytic reduction water to hydrogen has experienced considerable growth since end 1970s. Recently, with aim improving efficiency catalysis, single‐component photocatalysts have been developed in which photosensitizer is chemically coupled hydrogen‐evolving catalyst same molecule through a bridging ligand. Until now, none these operated efficiently pure aqueous solution: highly desirable medium energy‐conversion...
First principle calculations of extended X-ray absorption fine structure (EXAFS) data have seen widespread use in bioinorganic chemistry, perhaps most notably for modeling the Mn4Ca site oxygen evolving complex (OEC) photosystem II (PSII). The logic implied by rests on assumption that it is possible to a priori predict an accurate EXAFS spectrum provided underlying geometric correct. present study investigates extent which this using state art theory. FEFF program used evaluate ability...