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33 results on '"Organométalliques et catalyse : chimie et électrochimie moléculaires (OCCEM)"'

1. Optically tunable nonlinearities in polymers based on photoisomerizable metal-based coordination complexes

Author

Keitaro Nakatani, Lydie Viau, Sébastien Bidault, H. Le Bozec, Olivier Maury, Eléna Ishow, Sophie Brasselet, Joseph Zyss, Laboratoire de Photonique Quantique et Moléculaire ( LPQM ), École normale supérieure - Cachan ( ENS Cachan ) -CentraleSupélec-Centre National de la Recherche Scientifique ( CNRS ), Institut d'Alembert ( IDA ), Centre National de la Recherche Scientifique ( CNRS ) -École normale supérieure - Cachan ( ENS Cachan ), Organométalliques et catalyse : chimie et électrochimie moléculaires ( OCCEM ), Université de Rennes 1 ( UR1 ), Université de Rennes ( UNIV-RENNES ) -Université de Rennes ( UNIV-RENNES ) -Centre National de la Recherche Scientifique ( CNRS ), Laboratoire de Chimie - UMR5182 ( LC ), École normale supérieure - Lyon ( ENS Lyon ) -Université Claude Bernard Lyon 1 ( UCBL ), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique ( CNRS ), Laboratoire de Photophysique et Photochimie Supramoléculaires et Macromoléculaires ( PPSM ), École normale supérieure - Cachan ( ENS Cachan ) -Centre National de la Recherche Scientifique ( CNRS ), Laboratoire de Photonique Quantique et Moléculaire (LPQM), École normale supérieure - Cachan (ENS Cachan)-CentraleSupélec-Centre National de la Recherche Scientifique (CNRS), Institut d'Alembert (IDA), École normale supérieure - Cachan (ENS Cachan)-Centre National de la Recherche Scientifique (CNRS), Organométalliques et catalyse : chimie et électrochimie moléculaires (OCCEM), Centre National de la Recherche Scientifique (CNRS)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES), Laboratoire de Chimie - UMR5182 (LC), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), Laboratoire de Photophysique et Photochimie Supramoléculaires et Macromoléculaires (PPSM), École normale supérieure - Cachan (ENS Cachan)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Rennes (UR)-Centre National de la Recherche Scientifique (CNRS), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Materials science, TRANSFER RADICAL POLYMERIZATION, DIPOLAR, 02 engineering and technology, 010402 general chemistry, FILMS, 01 natural sciences, Biomaterials, Electrochemistry, INDUCED 2ND-HARMONIC GENERATION, Molecule, Organic chemistry, AZO-DYE POLYMERS, chemistry.chemical_classification, Quantitative Biology::Biomolecules, Poling, Doping, Second-harmonic generation, Polymer, Chromophore, 021001 nanoscience & nanotechnology, Condensed Matter Physics, 0104 chemical sciences, Electronic, Optical and Magnetic Materials, OCTUPOLAR MOLECULES, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Condensed Matter::Soft Condensed Matter, Dipole, chemistry, Coherent control, Chemical physics, ORIENTATIONAL MOBILITY, [ CHIM.THEO ] Chemical Sciences/Theoretical and/or physical chemistry, POLARIZATION HOLOGRAPHY, COHERENT CONTROL, CHROMOPHORES, 0210 nano-technology
Abstract

International audience; The bottom-up design of polymer films exhibiting quadratic nonlinear optical properties that can be tuned optically and chemically is described. The polymer matrices are doped with metal-containing chromophores built around a Zn-II core and photoisomerizable ligands with two different geometries. These molecules possess specifically designed photophysical and nonlinear optical properties to be used towards all-optical poling, an interference process between one- and two-photon excitations that locally induces macroscopic second-order effects in polymer films. It is shown that grafting the molecules onto the polymer chains improves the stability of the macroscopic photoinduced nonlinearity in the films.

Published
2006
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2. New 4,4′-oligophenylenevinylene functionalized-[2,2′]-bipyridyl chromophores: synthesis, optical and thermal properties

Author

Lydie Viau, Olivier Maury, Hubert Le Bozec, Organométalliques et catalyse : chimie et électrochimie moléculaires (OCCEM), and Université de Rennes (UR)-Centre National de la Recherche Scientifique (CNRS)

Subjects
bipyridines, Ligand, Chemistry, Organic Chemistry, Chromophore, Photochemistry, Biochemistry, Drug Discovery, Thermal, fluorophores, chromophores, [CHIM]Chemical Sciences, Organic chemistry, Absorption (electromagnetic radiation)
Abstract

International audience; The synthesis and characterization of new bipyridyl-based chromophores featuring extended oligophenylenevinylene π-conjugated backbones are reported. Their absorption and emission properties as well as their thermal stabilities are discussed in comparison to those of the parent ligand.

Published
2004
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3. Synthesis of a new bis-pyridyl crown-capped porphyrin

Author

Bernard Boitrel, Lydie Michaudet, Christian Ruzié, Institut de Chimie Moléculaire de l'Université de Bourgogne [Dijon] ( ICMUB ), Université de Bourgogne ( UB ) -Centre National de la Recherche Scientifique ( CNRS ), Institut de Chimie Moléculaire de l'Université de Bourgogne [Dijon] (ICMUB), Université de Bourgogne (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Organométalliques et catalyse : chimie et électrochimie moléculaires (OCCEM), and Université de Rennes (UR)-Centre National de la Recherche Scientifique (CNRS)

Subjects
inorganic chemicals, chemistry.chemical_classification, 010405 organic chemistry, Stereochemistry, organic chemicals, Organic Chemistry, 010402 general chemistry, [ CHIM ] Chemical Sciences, 01 natural sciences, Biochemistry, Porphyrin, 0104 chemical sciences, carbohydrates (lipids), chemistry.chemical_compound, chemistry, Drug Discovery, Polymer chemistry, polycyclic compounds, Nitro, [CHIM]Chemical Sciences, heterocyclic compounds, Crown ether
Abstract

International audience; The synthesis of a new porphyrin bearing both two pyridyl residues and two ortho-nitrophenyl groups in meso position is reported. The reduction of the nitro functions provides the points of anchoring for a crown ether maintained in a cofacial conformation.The synthesis of a new porphyrin bearing both two pyridyl residues and two ortho-nitrophenyl groups in meso position is reported. The reduction of the nitro functions provide the points of anchoring for a crown ether maintained in a cofacial conformation.

Published
2002
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4. Hydroxy-Functionalized Bipyridine and Tris(bipyridine)metal Chromophores: Synthesis and Optical Properties

Author

Jean-Paul Guégan, Hubert Le Bozec, Thomas Le Bouder, Olivier Maury, Lydie Viau, Organométalliques et catalyse : chimie et électrochimie moléculaires (OCCEM), and Université de Rennes (UR)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Tris, Organic Chemistry, chemistry.chemical_element, Chromophore, Ruthenium, Metal, chemistry.chemical_compound, Bipyridine, chemistry, visual_art, Polymer chemistry, visual_art.visual_art_medium, [CHIM]Chemical Sciences, Organic chemistry, Physical and Theoretical Chemistry, Homoleptic, Absorption (chemistry), Macromolecule
Abstract

A new family of symmetrically and unsymmetrically-substituted 4,4′-bis[(dialkylamino)styryl]-2,2′-bipyridine ligands, containing 1−4 hydroxy groups on their dialkylamino moieties, have been synthesized. They are readily prepared in good to excellent yields from 4,4′-dimethyl-2,2′-bipyridine and tetrahydropyranyloxy-protected [(hydroxyalkyl)amino]benzaldehydes. These chromophores display excellent thermal stabilities, with decomposition temperatures of up to 310 °C. The influence of the OH groups on the optical properties (absorption and emission) is discussed. The synthesis of the corresponding heteroleptic and homoleptic tris(bipyridine)metal(II) complexes (M2+ = Ru2+, Zn2+), as building blocks for the elaboration of macromolecular NLO-phores, is also described. (© Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)

Published
2002
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5. Proton nuclear magnetic resonance study of the binary complex of cytochrome P450cam and putidaredoxin: interaction and electron transfer rate analysis

Author

Christiane Jung, J. D. De Certaines, G. Hui Bon Hoa, Corinne Mouro, R.G.S. Spencer, Gérard Simonneaux, Arnaud Bondon, Université de Rennes (UR), Organométalliques et catalyse : chimie et électrochimie moléculaires (OCCEM), Université de Rennes (UR)-Centre National de la Recherche Scientifique (CNRS), Max Delbrück Center for Molecular Medicine [Berlin] (MDC), Helmholtz-Gemeinschaft = Helmholtz Association, Institut de biologie physico-chimique (IBPC (FR_550)), Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de résonance magnétique en biologie et en médecine, Université de Rennes (UR)-IFR91, National Institute on Aging [Baltimore, MD, USA] (NIH), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES), Centre National de la Recherche Scientifique (CNRS)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES), Centre National de la Recherche Scientifique (CNRS), and Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-IFR91

Subjects
Magnetic Resonance Spectroscopy, Camphor 5-Monooxygenase, Proton, Cytochrome, Macromolecular Substances, Isocyanide, Biophysics, Cytochrome P450, Heme, In Vitro Techniques, Photochemistry, Biochemistry, Redox, Nuclear magnetic resonance, Electron Transport, Electron transfer, 03 medical and health sciences, chemistry.chemical_compound, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Structural Biology, Enzyme Stability, Nitriles, Genetics, Magnetization transfer, Molecular Biology, ComputingMilieux_MISCELLANEOUS, 030304 developmental biology, 0303 health sciences, biology, 030302 biochemistry & molecular biology, Cell Biology, 3. Good health, Kinetics, chemistry, Proton NMR, biology.protein, Ferredoxins, Protons, Putidaredoxin
Abstract

A 1H nuclear magnetic resonance study of the complex of cytochrome P450cam-putidaredoxin has been performed. Isocyanide is bound to cytochrome P450cam in order to increase the stability of the protein both in the reduced and the oxidized state. Diprotein complex formation was detected through variation of the heme methyl proton resonances which have been assigned in the two redox states. The electron transfer rate at equilibrium was determinated by magnetization transfer experiments. The observed rate of oxidation of reduced cytochrome P450 by the oxidized putidaredoxin is 27 (±7) per s.

Published
1999
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6. Heteroleptic diimine copper(i) complexes with large extinction coefficients: synthesis, quantum chemistry calculations and physico-chemical properties

Author

Mateusz Rebarz, Fabrice Odobel, Martina Sandroni, Chantal Daniel, Huriye Akdas-Kilig, Hubert Le Bozec, Errol Blart, Yann Pellegrin, Megumi Kayanuma, Chimie Et Interdisciplinarité : Synthèse, Analyse, Modélisation (CEISAM), Université de Nantes - UFR des Sciences et des Techniques (UN UFR ST), Université de Nantes (UN)-Université de Nantes (UN)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Institut de Chimie de Strasbourg, Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire Avancé de Spectroscopie pour les Intéractions la Réactivité et l'Environnement - UMR 8516 (LASIRE), Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Centrale Lille Institut (CLIL), Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Organométalliques: Matériaux et Catalyse, Organométalliques et catalyse : chimie et électrochimie moléculaires (OCCEM), Centre National de la Recherche Scientifique (CNRS)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Centre National de la Recherche Scientifique (CNRS)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut des Sciences Chimiques de Rennes (ISCR), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Université de Nantes (UN)-Université de Nantes (UN)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Rennes (UR)-Centre National de la Recherche Scientifique (CNRS)-Université de Rennes (UR)-Centre National de la Recherche Scientifique (CNRS)-Institut des Sciences Chimiques de Rennes (ISCR), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National des Sciences Appliquées - Rennes (INSA Rennes)

Subjects
Coordination sphere, Absorption spectroscopy, 010405 organic chemistry, Ligand, Phenanthroline, chemistry.chemical_element, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, Electrochemistry, Photochemistry, 7. Clean energy, 01 natural sciences, Copper, Quantum chemistry, 0104 chemical sciences, Inorganic Chemistry, chemistry.chemical_compound, chemistry, Physical chemistry, Diimine
Abstract

International audience; : Using the HETPHEN approach, five new heteroleptic copper(i) complexes composed of a push-pull 4,4'-styryl-6,6'-dimethyl-2,2'-bipyridine ligand and a bulky bis[(2-diphenylphosphino)phenyl]-ether (DPEphos) or a bis2,9-mesityl phenanthroline (Mes2Phen) were prepared and characterized by electronic absorption spectroscopy, electrochemistry, and TD-DFT calculations. These complexes exhibit very intense absorption bands in the visible region with extinction coefficient in the range of 5-7 × 10(4) M(-1) cm(-1). The analysis of the position, intensity and band shape indicates a strong contribution from an intra-ligand charge-transfer transition centered on the styrylbipyridine ligand along with MLCT transitions. These new complexes experimentally demonstrate that good light harvesting properties with bis-diimine copper(i) complexes are a reality if one chooses suitable ligands in the coordination sphere. This constitutes a milestone towards using bis-diimine copper(i) complexes for solar energy conversion (artificial photosynthesis and solar cells).

Published
2013
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7. Synthesis and characterization of ruthenium (II) carbonyl complexes containing naphthyridine and acetylacetonate ligands and their catalytic activity in the hydrogen transfer reaction

Author

Hubert Le Bozec, Véronique Guerchais, Juana Gajardo, Loïc Toupet, Juan Carlos Araya, Pedro Aguirre, Sergio A. Moya, Universidad de Santiago de Chile, Universidad de Santiago de Chile [Santiago] (USACH), Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Organométalliques: Matériaux et Catalyse, Organométalliques et catalyse : chimie et électrochimie moléculaires (OCCEM), Centre National de la Recherche Scientifique (CNRS)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Centre National de la Recherche Scientifique (CNRS)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut des Sciences Chimiques de Rennes (ISCR), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut de Physique de Rennes (IPR), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Centre National de la Recherche Scientifique (CNRS), Universidad de Chile, ECOS-CONICYT [CO7E02], CONICYT-Chile, Fondecyt-Chile [1120685], Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Rennes (UR)-Centre National de la Recherche Scientifique (CNRS)-Université de Rennes (UR)-Centre National de la Recherche Scientifique (CNRS)-Institut des Sciences Chimiques de Rennes (ISCR), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Université de Rennes (UR)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Denticity, Stereochemistry, chemistry.chemical_element, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, Transfer hydrogenation, 01 natural sciences, Medicinal chemistry, Catalysis, Inorganic Chemistry, chemistry.chemical_compound, 8-Naphthyridine, Materials Chemistry, Physical and Theoretical Chemistry, Carbon monoxide, Acetophenone, Acetylacetonate complexes, 010405 organic chemistry, Hydrogen transfer, 3. Good health, 0104 chemical sciences, Ruthenium, chemistry, Single crystal, Ruthenium(II)
Abstract

International audience; A series of novel complexes of the Ru(L)(2)(CO)(2) L = 2-(3' methoxyphenyl)-1,8-naphthyridine (complex 1), and type Ru(acac)(2)(L)(CO) with L = 2-(3' methoxyphenyl)-1,8-naphthyridine (complex 2), 2-(2'-bromophenyl)-1,8-naphthyridine (complex 3) and 2-phenyl-1,8-naphthyridine (complex 4) was synthesized and characterized. We found that the complexes 2, 3, and 4 can be directly synthesized from Ru-3(CO)(12). The complex Ru(acac)(2)(L)(CO) L = 2-(3' methoxyphenyl)-1,8-naphthyridine (2) was characterized by X-ray single crystal analysis which confirms the monodentate coordination mode of the 1,8-naphthyridine derivate and the cis arrangement of the acac ligands. Preliminary studies in transfer hydrogenation of acetophenone in the presence of 2-propanol show the good catalytic activity of complex 2 with 92% conversion. (C) 2012 Elsevier B.V. All rights reserved.

Published
2013
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8. The First Hexadithienylethene‐Substituted Tris(bipyridine)metal Complexes as Quadratic NLO Photoswitches: Combined Experimental and DFT Studies

Author

Abdou Boucekkine, Véronique Guerchais, Anu Singh, Vincent Aubert, Lucie Ordronneau, Denis Jacquemin, Isabelle Ledoux, Hubert Le Bozec, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Laboratoire de Chimie - UMR5182 (LC), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), Laboratoire de Photonique Quantique et Moléculaire (LPQM), École normale supérieure - Cachan (ENS Cachan)-CentraleSupélec-Centre National de la Recherche Scientifique (CNRS), Organométalliques: Matériaux et Catalyse, Organométalliques et catalyse : chimie et électrochimie moléculaires (OCCEM), Centre National de la Recherche Scientifique (CNRS)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Centre National de la Recherche Scientifique (CNRS)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut des Sciences Chimiques de Rennes (ISCR), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Thérapie des maladies du muscle strié, Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Chimie Et Interdisciplinarité : Synthèse, Analyse, Modélisation (CEISAM), Université de Nantes - UFR des Sciences et des Techniques (UN UFR ST), Université de Nantes (UN)-Université de Nantes (UN)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), European Research Council Région des Pays de la Loire. Grant Number: Marches-278845 GENCI-CINES/IDRIS. Grant Number: c2012085117, Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Rennes (UR)-Centre National de la Recherche Scientifique (CNRS)-Université de Rennes (UR)-Centre National de la Recherche Scientifique (CNRS)-Institut des Sciences Chimiques de Rennes (ISCR), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Université de Nantes (UN)-Université de Nantes (UN)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Tris, photochrome, Nonlinear optics, Metal ions in aqueous solution, metal complexes, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 01 natural sciences, Catalysis, Coordination complex, Metal, Bipyridine, chemistry.chemical_compound, octupoles, Diarylethene, Computational chemistry, chemistry.chemical_classification, dipoles, density functional calulations, 010405 organic chemistry, Organic Chemistry, General Chemistry, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Crystallography, chemistry, visual_art, visual_art.visual_art_medium, coordination chemistry, diarylethene, Density functional theory, photochromes
Abstract

International audience; This article discusses the second-order nonlinear optical properties of a series of dipolar bis(dibutylaminostyryl) bipyridine M(II) dichloride complexes (M = Co, Ni, Cu, Zn) and octupolar tris(bipyridine) M(II) complexes of D3 symmetry (M = Fe, Ru, Os, Ni, Cu, Zn). Their quadratic NLO-susceptibilities have been determined by the Harmonic Light Scattering technique at 1.91 μm. This study shows that the optical and NLO properties are strongly influenced by the nature of the metallic centers, and the first hyperpolarizability constants β can be fine tuned by varying the nature of the metal ion. Finally, we describe an efficient strategy for the design of switchable nonlinear optical (NLO) materials. For that purpose, we have used a photochromic metal complexes which gives rise to an efficient ON/OFF reversible switching of the μβ values determined by EFISH at 1.91μm.

Published
2012
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9. Molecular tweezers: Synthesis and formation of host-guest complexes

Author

Loïc Toupet, Jean-François Cupif, Pierre van de Weghe, Maud Gayral, Philippe Uriac, Nicolas Levoin, Béatrice Legouin, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire Bioprojet, Organométalliques et catalyse : chimie et électrochimie moléculaires (OCCEM), Université de Rennes (UR)-Centre National de la Recherche Scientifique (CNRS), Université de Rennes 1, Région Bretagne, Rennes Métropole, Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Centre National de la Recherche Scientifique (CNRS)-Université de Rennes 1 (UR1), and Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)

Subjects
chemistry.chemical_classification, Ketone, 010405 organic chemistry, Stereochemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Organic Chemistry, Supramolecular chemistry, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Inclusion compound, chemistry.chemical_compound, Molecular recognition, chemistry, Host-guest systems, Sandwich compound, Tweezers, Polymer chemistry, Pi interactions, Molecule, Physical and Theoretical Chemistry, Molecular tweezers
Abstract

International audience; A chiral molecular tweezer obtained from (+)-usnic acid placed in solution in the presence of various aromatic compounds afforded complexes with low association constants. Thus, the X-ray structure of assembly 3i is presented, where the guest is sandwiched between the two pincers of the tweezer. The association constants for various guests were determined through different methods. Finally, other tweezers with electron-rich aromatic aldehydes and ketones were prepared from (1R,2R)-1,2-diaminocyclohexane. The most interesting complexes were also confirmed through structural analysis, and the best results were obtained with 10-hydroxyphenanthrene-9-carbaldehyde (5i) as the aromatic moiety.

Published
2010
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10. Metal-Based Quadratic Nonlinear Optical Materials

Author

Hubert Le Bozec, Olivier Maury, Laboratoire de Chimie - UMR5182 (LC), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Organométalliques: Matériaux et Catalyse, Organométalliques et catalyse : chimie et électrochimie moléculaires (OCCEM), Université de Rennes (UR)-Centre National de la Recherche Scientifique (CNRS)-Université de Rennes (UR)-Centre National de la Recherche Scientifique (CNRS)-Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), Centre National de la Recherche Scientifique (CNRS)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Centre National de la Recherche Scientifique (CNRS)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Electromagnetic field, chemistry.chemical_classification, 3D optical data storage, Fine-tuning, Signal processing, Materials science, 010405 organic chemistry, business.industry, Image processing, Polymer, 010402 general chemistry, 01 natural sciences, Ray, 0104 chemical sciences, chemistry, Optoelectronics, [CHIM]Chemical Sciences, Photonics, business, ComputingMilieux_MISCELLANEOUS
Abstract

Nonlinear optical (NLO) materials have been the focus of intensive investigations for several decades from both the fundamental and practical points of view for their possible applications in the domain of optoelectronics and photonics. NLO materials can be used to manipulate optical signals, and when light interacts with such materials the incident light can be changed and new electromagnetic field components generated. NLO materials have potential applications in optical signal processing, frequency generation such as second and third harmonic generation (SHG and THG, respectively), and can also contribute to optical data storage and image processing. NLO activity can be found in inorganic crystals, such as LiNbO3, and also in organic materials. The latter have attracted great interest owing to their fast and large nonlinearities, their inherent tailorability, which allows fine tuning of the NLO properties, and to their compatibility with polymer matrices. About twenty years ago, the field of NLO was extended to molecular materials featuring organometallic and coordination complexes.

Published
2010
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11. New bichromophoric-2,20-bipyridines: synthesis and optical properties

Author

Le Bozec, Hubert, Maury, Olivier, Lohio, Olivier, Viau, Lydie, Organométalliques et catalyse : chimie et électrochimie moléculaires (OCCEM), Université de Rennes (UR)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie - UMR5182 (LC), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), and Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)

Subjects
[CHIM.ORGA]Chemical Sciences/Organic chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry
Abstract

International audience; The synthesis and characterization of new unsymmetrically substituted bipyridyl-based chromophores featuring p-con- jugated donor, acceptor or photoisomerizable backbones are reported. Their absorption and emission properties are discussed in comparison to those of the parent ligands.

Published
2007
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12. Mixed-Metal Cluster Chemistry. 29. Core Expansion and Ligand-Driven Metal Exchange at Group 6−Iridium Clusters

Author

Usher, Alistair, Lucas, Nigel, Dalton, G. T., Randles, Michael, Viau, Lydie, Humphrey, Mark, Willis, Anthony, Petrie, Simon, Stranger, Robert, Rae, David, Australian National University (ANU), Organométalliques et catalyse : chimie et électrochimie moléculaires (OCCEM), Centre National de la Recherche Scientifique (CNRS)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Université de Rennes (UR)-Centre National de la Recherche Scientifique (CNRS), and Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Mixed-metal cluster, molybdenum, iridium, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, core expansion
Abstract

International audience; We report herein syntheses of medium-nuclearity very-mixed metal clusters by an unusual combination of core expansion and metal exchange upon reacting MIr3(CO)11(è-L) (M ) Mo, W; L ) C5H5,C5HMe4,C5Me5) with [M(CO)3(è-L)]- (M ) Mo, W; L ) C5HMe4,C5Me5), the metal exchange being a remarkable “ligand-driven” process, together with comprehensive theoretical, structural, and spectroscopic studies of the resultant species, and studies clarifying aspects of the reaction mechanism.

Published
2006
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13. Synthesis, structural studies, theoretical calculations, and linear and nonlinear optical properties of terpyridyl lanthanide complexes: new evidence for the contribution of f electrons to the NLO activity

Author

Loïc Toupet, J. A. Gareth Williams, Joseph Zyss, Isabelle Ledoux, Katell Senechal-David, Hubert Le Bozec, Nicolas Tancrez, Abdou Boucekkine, Anne Hémeryck, Olivier Maury, Jean-Paul Guégan, Organométalliques et catalyse : chimie et électrochimie moléculaires (OCCEM), Centre National de la Recherche Scientifique (CNRS)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES), Laboratoire de Chimie du solide et inorganique moléculaire (LCSIM), Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES), Laboratoire de Photonique Quantique et Moléculaire (LPQM), École normale supérieure - Cachan (ENS Cachan)-CentraleSupélec-Centre National de la Recherche Scientifique (CNRS), Groupe matière condensée et matériaux (GMCM), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Centre National de la Recherche Scientifique (CNRS), Department of Chemistry, Durham University, Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR), Université de Rennes (UR)-Centre National de la Recherche Scientifique (CNRS), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)

Subjects
Lanthanide, 010405 organic chemistry, Stereochemistry, Hyperpolarizability, chemistry.chemical_element, General Chemistry, Nuclear magnetic resonance spectroscopy, Yttrium, Time-dependent density functional theory, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 7. Clean energy, 01 natural sciences, Biochemistry, Catalysis, 0104 chemical sciences, Ion, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Colloid and Surface Chemistry, chemistry, Intramolecular force, Physical chemistry, Isostructural
Abstract

International audience; The synthesis and structural, photophysical, and second-order nonlinear optical (NLO) properties of a novel lanthanide terpyridyl-like complex family LLn(NO(3))(3) (Ln = La, Gd, Dy, Yb, and Y) are reported. The isostructural character of this series in solution and in the solid state has been established on the basis of X-ray diffraction analysis in the cases of yttrium and gadolinium complexes, theoretical optimization of geometry (DFT), and NMR spectroscopy. The absorption, emission, and solvatochromic properties of the free terpyridyl-like ligand L were thoroughly investigated, and the twist intramolecular charge transfer (TICT) character of the lowest energy transition was confirmed by theoretical calculation (TDDFT and CIS). The similar ionochromic effect of the different lanthanide ions was evidenced by the similar UV-visible spectra of the complete family of complexes. On the other hand, the quadratic hyperpolarizability coefficient beta, measured by the harmonic light scattering (HLS) technique, is clearly dependent on the nature of the metal, and a careful examination of the particular case of yttrium unambiguously confirms the contribution of metal f electrons to the NLO activity.

Published
2006
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14. Photoisomerizable Bipyridine Ligands and Macroligands: Absorption, Photoisomerization Properties and Theoretical Study

Author

Loïc Toupet, Karine Costuas, Hubert Le Bozec, Stéphanie Boulin, Lydie Viau, Itamar Malkowsky, Eléna Ishow, Olivier Maury, Keitaro Nakatani, Organométalliques et catalyse : chimie et électrochimie moléculaires (OCCEM), Université de Rennes (UR)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie du solide et inorganique moléculaire (LCSIM), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR), Groupe matière condensée et matériaux (GMCM), Laboratoire de Photophysique et Photochimie Supramoléculaires et Macromoléculaires (PPSM), École normale supérieure - Cachan (ENS Cachan)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie - UMR5182 (LC), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES), Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC)

Subjects
Azo compound, Photoisomerization, azo compounds, 010405 organic chemistry, bipyridine ligands, photoisomerization, Crystal structure, 010402 general chemistry, Photochemistry, 01 natural sciences, Atomic and Molecular Physics, and Optics, Cis trans isomerization, 0104 chemical sciences, chemistry.chemical_compound, Crystallography, Bipyridine, chemistry, Polymerization, polymerization, density functional calculations, Molecule, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], Physical and Theoretical Chemistry, Isomerization
Abstract

Two 2,2'-bipyridines, substituted at the 4,4'-positions by p-dialkylaminophenylazostyryl moieties p-R 2 N-C 6 H 4 -N=N-C 6 H 4 -CH=H-16 a, R 2 N=nBu 2 N; 6b, R 2 N=(nBu)(C 4 H 8 OTHP)N; 6c, R 2 N= (nBu)(C 4 H 8 OH)NJ, were successfully synthesized by using Wadworth-Emmons reactions. The X-ray structure of 6a has been determined. Esterification of 6c with 2-bromoisobutyroylbromide afforded 6d. This ligand was used as an initiator for the living radical polymerization of methylmethacrylate (MMA) and gave rise to macroligand 6e. Thin films of good optical quality were obtained by the spin-coating technique. Photoisomerization experiments were carried out on 6a in solution and on 6e in both solution and film, and the kinetics of photochemical (E/Z) and thermal (Z/E) isomerization were investigated. They were found to show Z-E back isomerization typical of aminoazobenzene-type rather than of push-pull-type molecules. Density functional theoretical (TD-DFT) calculations were performed on model compound 6 a' (R 2 N=Me 2 N) to understand the structural and electronic transitions of the corresponding E-E, E-Z and Z-Z isomers. It was found that the E-E isomer is almost planar as observed experimentally by X-ray diffraction, whereas the Z-Z isomer, which is 35.4 kcal mol -1 less stable than the E-E isomer, is nonplanar. The theoretical studies also reveal that several transitions of π-π*, n-π* and charge-transfer (CT) types, are involved in the long-wavelength transition of 6a (E-E). The same observations can be made for the (Z-Z) isomer, and the TD-DFT simulated spectrum fits quite nicely to the experimental, reproducing and explaining the apparition of a blue-shifted charge-transfer band at 390 nm.

Published
2006
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15. Tandem Catalytic Carbene Addition/Bicyclization of Enynes. One-Step Synthesis of Fluorinated Bicyclic Amino Esters by Ruthenium Catalysis

Author

Loic Toupet, Sylvie Dérien, Igor D. Titanyuk, Grigorii T. Shchetnikov, Serguej N. Osipov, Matthieu Eckert, Pierre H. Dixneuf, Florian Monnier, Organométalliques et catalyse : chimie et électrochimie moléculaires (OCCEM), Université de Rennes (UR)-Centre National de la Recherche Scientifique (CNRS), Groupe matière condensée et matériaux (GMCM), Centre National de la Recherche Scientifique (CNRS)-Université de Rennes 1 (UR1), and Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)

Subjects
Amino esters, Enyne, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Organic Chemistry, chemistry.chemical_element, [CHIM.CATA]Chemical Sciences/Catalysis, General Medicine, 010402 general chemistry, Metathesis, Biochemistry, 01 natural sciences, Medicinal chemistry, Reductive elimination, 0104 chemical sciences, Ruthenium, chemistry.chemical_compound, Ring-closing metathesis, chemistry, Organic chemistry, Moiety, Diazo, Physical and Theoretical Chemistry
Abstract

International audience; The reaction of diazo compounds with enynes, containing a fluorinated amino acid moiety, in the presence of the precatalyst Cp*(Cl)Ru(COD) leads to fluorinated alkenyl bicyclo[3.1.0]hexane and [4.1.0]heptane amino acid derivatives. It is remarkable that the catalyst, in situ generated from ruthenium complex and diazo compound, completely inhibits the ring closing metathesis of enyne to the profit of tandem alkenylation/cyclopropanation with high stereoselectivity. The study shows that the Cp*(Cl)Ru moiety in ruthenacyclobutane favors reductive elimination versus expected alkene metathesis.

Published
2006
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16. Bonding and Substituent Effects in Electron-Rich Mononuclear Ruthenium σ-Arylacetylides of the Formula [(η2-dppe)(η5-C5Me5)Ru(CC)-1,4-(C6H4)X][PF6]n (n = 0, 1; X = NO2, CN, F, H, OMe, NH2)

Author

Paul, Frédéric, Ellis, Benjamin G., Bruce, Michael I., Toupet, Loic, Roisnel, Thierry, Costuas, Karine, Halet, Jean-François, Lapinte, Claude, Organométalliques et catalyse : chimie et électrochimie moléculaires (OCCEM), Université de Rennes (UR)-Centre National de la Recherche Scientifique (CNRS), University of Adelaide, Groupe matière condensée et matériaux (GMCM), Laboratoire de Chimie du solide et inorganique moléculaire (LCSIM), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR), Centre National de la Recherche Scientifique (CNRS)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES), Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Université de Rennes 1 (UR1), and Université de Rennes (UNIV-RENNES)

Subjects
[CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, [CHIM.INOR]Chemical Sciences/Inorganic chemistry
Abstract

International audience; This study reports the isolation and the structural (X-ray), UV−vis, and NMR characterization of a series of electron-rich Ru(II) acetylide complexes of the formula (η2-dppe)(η5-C5Me5)Ru(CC)-1,4-(C6H4)X (1a−f; X = NO2, CN, F, H, OMe, NH2) and (η2-dppe)(η5-C5Me5)Ru(CC)-1,3-(C6H4)F (1c-m), as well as the spectroscopic (near-IR and ESR) in situ characterization of the corresponding elusive Ru(III) radical cations. The spectroscopic data are discussed in connection with DFT computations, and a consistent picture of the electronic structure of these Ru(II) and Ru(III) acetylide complexes is proposed. Notably, the strong reactivity of the Ru(III) radicals evidenced in this contribution constitutes a major difference with the relative stability of the known iron analogues.

Published
2006
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17. Synthesis of star-shaped metallo-polymeric chromophores by atom transfer radical polymerization

Author

Hubert Le Bozec, Olivier Maury, David M. Haddleton, Lydie Viau, Michael Even, Organométalliques et catalyse : chimie et électrochimie moléculaires (OCCEM), Centre National de la Recherche Scientifique (CNRS)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Laboratoire Logiciels Systèmes Réseaux (LSR - IMAG), Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique de Grenoble (INPG)-Université Joseph Fourier - Grenoble 1 (UJF), Laboratoire de Chimie - UMR5182 (LC), Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École normale supérieure - Lyon (ENS Lyon)-Institut de Chimie du CNRS (INC), UMR 212 EME 'écosystèmes marins exploités' (EME), Institut de Recherche pour le Développement (IRD)-Institut Français de Recherche pour l'Exploitation de la Mer (IFREMER)-Université de Montpellier (UM), Organométalliques: Matériaux et Catalyse, Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Centre National de la Recherche Scientifique (CNRS)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut des Sciences Chimiques de Rennes (ISCR), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Université de Rennes (UR)-Centre National de la Recherche Scientifique (CNRS), Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université Joseph Fourier - Grenoble 1 (UJF)-Institut National Polytechnique de Grenoble (INPG)-Centre National de la Recherche Scientifique (CNRS), École normale supérieure de Lyon (ENS de Lyon)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Rennes (UR)-Centre National de la Recherche Scientifique (CNRS)-Université de Rennes (UR)-Centre National de la Recherche Scientifique (CNRS)-Institut des Sciences Chimiques de Rennes (ISCR), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National des Sciences Appliquées - Rennes (INSA Rennes)

Subjects
General Chemical Engineering, Bipyridine ligands, Radical polymerization, 02 engineering and technology, ATRP, Star polymers, 010402 general chemistry, 01 natural sciences, Coordination complex, chemistry.chemical_compound, Polymer chemistry, Methyl methacrylate, chemistry.chemical_classification, Atom-transfer radical-polymerization, Solution polymerization, General Chemistry, Polymer, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, Chromophores, 0104 chemical sciences, Coordination chemistry, Monomer, chemistry, 0210 nano-technology, Luminescence
Abstract

The synthesis of bromoester-functionalized dialkylaminostyryl-2,2′-bipyridyl ligands and of the corresponding tris[dialkylaminostyryl-2,2′-bipyridine] metal(II) complexes are reported (M = Fe, Ru, Zn). These complexes are used as multifunctional metallo-initiators for the atom transfer radical polymerization (ATRP) of methyl methacrylate. The resulting new star-shaped polymers combine the optical (UV–visible and luminescence) properties of the monomers with good processability, which allow to build high optical quality thin films by the spin-coating technique. To cite this article: L. Viau et al., C. R. Chimie 8 (2005).

Published
2005
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18. Mixed-metal cluster chemistry. 28. Core enlargement of tungsten-iridium clusters with alkynyl, ethynediyl and butadiynediyl reagents

Author

Susan M. Waterman, Rachel L. Roberts, Mark G. Humphrey, Brian W. Skelton, Michael I. Bruce, Anthony C. Willis, Paul J. Low, Gulliver T. Dalton, Allan H. White, George A. Koutsantonis, Lydie Viau, Australian National University (ANU), Organométalliques et catalyse : chimie et électrochimie moléculaires (OCCEM), Centre National de la Recherche Scientifique (CNRS)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Université de Rennes (UR)-Centre National de la Recherche Scientifique (CNRS), and Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Mixed metal, Chemistry, Stereochemistry, Cluster chemistry, chemistry.chemical_element, Tungsten, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, Triple bond, Inorganic Chemistry, Crystallography, Reagent, Cluster (physics), Iridium, Physical and Theoretical Chemistry, Bond cleavage
Abstract

Reaction of [WIr3(mu-CO)3(CO)8(eta-C5Me5)] (1c) with [W(C[triple bond]CPh)(CO)3(eta-C5H5)] afforded the edge-bridged tetrahedral cluster [W2Ir3(mu4-eta2-C2Ph)(mu-CO)(CO)9(eta-C5H5)(eta-C5Me5)] (3) and the edge-bridged trigonal-bipyramidal cluster [W3Ir3(mu4-eta2-C2Ph)(mu-eta2-C=CHPh)(Cl)(CO)8(eta-C5Me5)(eta-C5H5)2] (4) in poor to fair yield. Cluster 3 forms by insertion of [W(C[triple bond]CPh)(CO)3(eta-C5H5)] into Ir-Ir and W-Ir bonds, accompanied by a change in coordination mode from a terminally bonded alkynyl to a mu4-eta2 alkynyl ligand. Cluster 4 contains an alkynyl ligand interacting with two iridium atoms and two tungsten atoms in a mu4-eta2 fashion, as well as a vinylidene ligand bridging a W-W bond. Reaction of [WIr3(CO)11(eta-C5H5)] (1a) or 1c with [(eta-C5H5)(CO)2 Ru(C[triple bond]C)Ru(CO)2(eta-C5H5)] afforded [Ru2WIr3(mu5-eta2-C2)(mu-CO)3(CO)7(eta-C5H5)2(eta-C5R5)] [R = H (5a), Me (5c)] in low yield, a structural study of 5a revealing a WIr3 butterfly core capped and spiked by Ru atoms; the diruthenium ethyndiyl precursor has undergone Ru-C scission, with insertion of the C2 unit into a W-Ir bond of the cluster precursor. Reaction of [W2Ir2(CO)10(eta-C5H5)2] with the diruthenium ethyndiyl reagent gave [RuW2Ir2{mu4-eta2-(C2C[triple bond]C)Ru(CO)2(eta-C5H5)}(mu-CO)2(CO)6(eta-C5H5)3] (6) in low yield, a structural study of 6 revealing a butterfly W2Ir2 unit capped by a Ru(eta-C5H5) group resulting from Ru-C scission; the terminal C2 of a new ruthenium-bound butadiyndiyl ligand has been inserted into the W-Ir bond. Reaction between 1a, [WIr3(CO)11(eta-C5H4Me)] (1b), or 1c and [(eta-C5H5)(CO)3W(C[triple bond]CC[triple bond]C)W(CO)3(eta-C5H5)] afforded [W2Ir3{mu4-eta2-(C2C[triple bond]C)W(CO)3(eta-C5H5)}(mu-CO)2(CO)2(eta-C5H5)(eta-C5R5)] [R = H (7a), Me (7c); R5 = H4Me (7b)] in good yield, a structural study of 7c revealing it to be a metallaethynyl analogue of 3.

Published
2005
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19. Organic and metal-catalyzed electrosynthesis

Author

Moinet, Claude, Jutand, Anny, Organométalliques et catalyse : chimie et électrochimie moléculaires (OCCEM), Centre National de la Recherche Scientifique (CNRS)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES), Processus d'Activation Sélective par Transfert d'Energie Uni-électronique ou Radiatif (UMR 8640) (PASTEUR), Université Pierre et Marie Curie - Paris 6 (UPMC)-Département de Chimie - ENS Paris, École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Gérard Genner, Université de Rennes (UR)-Centre National de la Recherche Scientifique (CNRS), Département de Chimie - ENS Paris, École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS-PSL), and Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)

Subjects
[CHIM.CATA]Chemical Sciences/Catalysis
Published
2005

20. All-Optical Orientation of Photoisomerizable Octupolar Zinc(II) Complexes in Polymer Films

Author

Eléna Ishow, Lydie Viau, Isabelle Ledoux, Joseph Zyss, Olivier Maury, Sébastien Bidault, Sophie Brasselet, Hubert Le Bozec, Keitaro Nakatani, Organométalliques et catalyse : chimie et électrochimie moléculaires (OCCEM), Université de Rennes (UR)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Photonique Quantique et Moléculaire (LPQM), École normale supérieure - Cachan (ENS Cachan)-CentraleSupélec-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Photophysique et Photochimie Supramoléculaires et Macromoléculaires (PPSM), and École normale supérieure - Cachan (ENS Cachan)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
chemistry.chemical_classification, Nonlinear optics, Photoisomerization, Atom-transfer radical-polymerization, Ligand, Thin films, Polymer films, chemistry.chemical_element, General Chemistry, Zinc, Polymer, Chromophores, Ligands, Biochemistry, Catalysis, Cis trans isomerization, Bipyridine, chemistry.chemical_compound, Colloid and Surface Chemistry, chemistry, Polymer chemistry, Organic chemistry, [CHIM]Chemical Sciences, Methyl methacrylate
Abstract

International audience; A new type of 4,4‘-bis(styryl)-2,2‘-bipyridine functionalized by a dialkylamino-azobenzene group has been prepared. This ligand has allowed the preparation of photoisomerizable octupolar tris(bipyridyl)zinc(II) complexes and the corresponding star-shaped polymer by atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA). The photoisomerization properties of such new metallo-chromophores have been studied. The macroscopic molecular orientation of the corresponding doped and grafted NLO-polymer films is reported for the first time.

Published
2004
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21. Ruthenium-Catalyzed C–C Bond Formation

Author

Monnier, Florian, Dérien, Sylvie, Dixneuf, Pierre H., Organométalliques et catalyse : chimie et électrochimie moléculaires (OCCEM), Centre National de la Recherche Scientifique (CNRS)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES), and Université de Rennes (UR)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Ruthenium catalysts · C–C and C=C bond formation · Alkenes · Alkynes · Allyl ruthenium · Ruthenacycle · Hydroruthenation, [CHIM.ORGA]Chemical Sciences/Organic chemistry, [CHIM.CATA]Chemical Sciences/Catalysis
Abstract

Molecular ruthenium catalysts are now currently used to perform selective carbon– carbon bond formation by combination of simple substrates. Their tolerance toward functional groups has allowed the access to high value,multifunctional molecules. It will be shown that ruthenium catalysts allow the coupling of functional alkenes or alkynes with a variety of unsaturated molecules such as alkenes, dienes, alkynes, and diynes. A large range of electron-rich ruthenium or hydridoruthenium complexes are currently used for the formation of cyclic and polycyclic compounds on reaction with substrates containing several unsaturated C–C bonds. Ruthenium complexes have promoted several original activation pathways, such as C–H bond activation, the distribution of carbene from diazoalkanes, and especially their versatility in making a large variety of ruthenacycle intermediates. Besides the applications of ruthenium precatalysts in organic synthesis an important discussion of and mechanisms will be presented.

Published
2004
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22. Biscarbene-Ruthenium Complexes in Catalysis: Novel Stereoselective Synthesis of (1E,3E)-1,4-Disubstituted-1,3-dienes via Head-to-Head Coupling of Terminal Alkynes and Addition of Carboxylic Acids

Author

Odile Eisenstein, Sylvie Dérien, Eric Clot, Pierre H. Dixneuf, Jacques Le Paih, Florian Monnier, Organométalliques et catalyse : chimie et électrochimie moléculaires (OCCEM), Centre National de la Recherche Scientifique (CNRS)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES), Laboratoire de structure et de dynamique des systèmes moléculaires et solides (LSDSMS), Université Montpellier 2 - Sciences et Techniques (UM2)-Centre National de la Recherche Scientifique (CNRS), and Université de Rennes (UR)-Centre National de la Recherche Scientifique (CNRS)

Subjects
chemistry.chemical_classification, ONIOM, Double bond, 010405 organic chemistry, Stereochemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Carboxylic acid, Alkyne, Protonation, General Medicine, General Chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, 010402 general chemistry, 01 natural sciences, Biochemistry, Medicinal chemistry, Catalysis, 0104 chemical sciences, chemistry.chemical_compound, Colloid and Surface Chemistry, Dicarboxylic acid, chemistry, Carbene
Abstract

International audience; The reaction of a variety of alkynes RCCH with a variety of carboxylic acids R1CO2H, in the presence of 5% of RuCl(COD)C5Me5, selectively leads to the dienylesters (1E,3E)-RCH1=CH2-CH3=C(R)(O2CR1). The reaction also applies to amino acid and dicarboxylic acid derivatives. It is shown that the first step of the reaction consists of the head-to-head alkyne coupling and of the formation of the metallacyclic biscarbene-ruthenium complex (C5Me5)(Cl)Ru:C(R)-CH=CH-C:(R), isolated for R = Ph and catalyzing the formation of dienylester. D-labeled reactions show that the alkyne protons remain at the alkyne terminal carbon atoms and carboxylic acid protonates the C1 carbon atom. QM/MM (ONIOM) calculations, supporting a mixed Fischer-Schrock-type biscarbene complex, show that protonation occurs preferentially at the carbene carbon C1 adjacent to Ru, in the relative cis position with respect to the Ru-Cl bond, to give a mixed C(1)alkyl-C(4)carbene complex in which the C4 carbene is conjugated with the noncoordinated C2=C3 double bond. This 16-electron intermediate has a weak stabilizing agostic C-H bond. This most stable isomer appears to have a C4 center more accessible to the nucleophilic addition which accounts for the experimentally observed product.

Published
2003
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23. Addition of Diazoalkanes to Enynes Promoted by a Ruthenium Catalyst: Simple Synthesis of Alkenyl Bicyclo[3.1.0]hexane Derivatives

Author

Florian Monnier, Sylvie Dérien, Pierre H. Dixneuf, Dante Castillo, Loïc Toupet, Organométalliques et catalyse : chimie et électrochimie moléculaires (OCCEM), Centre National de la Recherche Scientifique (CNRS)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES), Groupe matière condensée et matériaux (GMCM), and Université de Rennes (UR)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Bicyclic molecule, Chemistry, Cyclopropanation, 010405 organic chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, chemistry.chemical_element, One-Step, Ruthenium catalyst, General Chemistry, General Medicine, [CHIM.CATA]Chemical Sciences/Catalysis, 010402 general chemistry, Medicinal chemistry, 01 natural sciences, Catalysis, Ruthenium, 0104 chemical sciences, 3. Good health, Hexane, chemistry.chemical_compound, Organic chemistry, Stereoselectivity, cyclization • diazo compounds • enynes • heterocycles • ruthenium, Cyclooctadiene
Abstract

International audience; [Cp*RuCl(cod)] (Cp * =C5Me5, cod=cyclooctadiene) promotes the reaction of 1,6- enynes with an excess of diazoalkane in dioxane in one step to afford selectively 1-alkenyl bicyclo[3.1.0]hexane derivatives (see scheme, X=O, NTs; Y=CO2Et; R1=H, Me; R2=H; Ts=p-toluenesulfonyl). This novel reaction involves the stereoselective formation of three CC bonds and a cyclopropanation step.

Published
2003
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24. Synthesis of an organometallic complex - The allenylidene trans-[Cl(dppe)(2)Ru-II=C=C-CPh2](+),PF6

Author

Touchard, D, Hissler, M, Rigaut, Stéphane, Organométalliques et catalyse : chimie et électrochimie moléculaires (OCCEM), Université de Rennes (UR)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES), and Rigaut, Stéphane

Subjects
[CHIM] Chemical Sciences, [CHIM]Chemical Sciences
Abstract

International audience; Organometallic synthesis, using standard Schlenk techniques, and characterization of an allenylidene ruthenium complex.

Published
2003

25. New Star-Shaped Metallo-Polymeric Chromophores

Author

Michael Even, Lydie Viau, Hubert Le Bozec, David M. Haddleton, Olivier Maury, Organométalliques et catalyse : chimie et électrochimie moléculaires (OCCEM), Université de Rennes (UR)-Centre National de la Recherche Scientifique (CNRS), Department of Chemistry [University of Warwick], and University of Warwick [Coventry]

Subjects
chemistry.chemical_classification, Polymers and Plastics, Atom-transfer radical-polymerization, Organic Chemistry, Radical polymerization, chemistry.chemical_element, Polymer, Zinc, Chromophore, Bipyridine, chemistry.chemical_compound, chemistry, Polymer chemistry, Materials Chemistry, [CHIM]Chemical Sciences, Thermal stability, Methyl methacrylate
Abstract

International audience; The synthesis of new star-shaped polymers, prepared by atom transfer radical polymerization of methyl methacrylate with tris(dialkylaminostyryl-2,2′-bipyridine) zinc(II) and iron(II) metalloinitiators, is reported. Their thermal and optical (absorption and emission) properties are discussed.

Published
2003
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26. Enamine-Functionalized Oligopyridines as Convenient Intermediates for the Synthesis of Carbaldehyde Derivatives

Author

Olivier Maury, Katell Sénéchal, Lydie Viau, Hubert Le Bozec, Philippe Dupau, Jean-Paul Guégan, Loic Toupet, Organométalliques et catalyse : chimie et électrochimie moléculaires (OCCEM), Université de Rennes (UR)-Centre National de la Recherche Scientifique (CNRS), and Groupe matière condensée et matériaux (GMCM)

Subjects
heterocycles, ligands, Phenanthroline, Organic Chemistry, Regioselectivity, General Medicine, Chromophore, Acceptor, Combinatorial chemistry, Catalysis, Enamine, chemistry.chemical_compound, Bipyridine, chemistry, imines, aldehydes, Organic chemistry, Surface modification, chromophores, [CHIM]Chemical Sciences, Two-dimensional nuclear magnetic resonance spectroscopy
Abstract

International audience; A series of enamine-substituted bipyridine, biquinoline and o-phenanthroline chromophores has been synthesized and fully characterized. The para regioselectivity of the functionalization is discussed on the basis of 2D NOESY correlation and X-ray diffraction analysis. Absorption and emission spectroscopic studies allow a comparison of the acceptor strength of the heterocyclic core (biquinoline > phenanthroline > bipyridine). These enamine derivatives are key intermediates for a straightforward preparation of the corresponding dicarbaldehyde-bisimine compounds.

Published
2003
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27. Ruthenium Acetylide Oxidation: From Stable Radicals to Allenylidene Synthesis via -Elimination of H+

Author

Pierre H. Dixneuf, François Mousset, Stéphane Rigaut, Florian Monnier, and Daniel Touchard, Organométalliques et catalyse : chimie et électrochimie moléculaires (OCCEM), Centre National de la Recherche Scientifique (CNRS)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES), and Université de Rennes (UR)-Centre National de la Recherche Scientifique (CNRS)

Subjects
chemistry.chemical_classification, Base (chemistry), Proton, 010405 organic chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Acetylide, Radical, Organic Chemistry, Cationic polymerization, chemistry.chemical_element, 010402 general chemistry, Photochemistry, 01 natural sciences, Medicinal chemistry, 0104 chemical sciences, 3. Good health, Ruthenium, Inorganic Chemistry, chemistry.chemical_compound, chemistry, Physical and Theoretical Chemistry
Abstract

Oxidation of ruthenium(II) acetylides trans-[Cl(dppe)2Ru-CC-CHR2] (R = H, CH3, Ph) leads to cationic radicals of which the stability is found to be highly influenced by the nature of R. This oxidative process leads to a stable cationic radical (R = CH3, H) or to its rearrangement into a neutral radical, trans-[Cl(dppe)2Ru-CC-C(R)2] for R = Ph. This unprecedented -elimination of a proton provides both the allenylidene trans-[Cl(dppe)2Ru=C=C=CR2]PF6 and the vinylidene trans-[Cl(dppe)2Ru=C=CH-CHR2]PF6. The allenylidene can be selectively obtained from the acetylide in the presence of a base

Published
2002
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28. Reactivity of carbanions of Fischer-type carbene complexes with pyrylium salts. Synthesis and characterization of new gamma-methylenepyran carbene complexes via an addition-oxidation-deprotonation process

Author

Claude Moinet, Françoise Robin-le Guen, Nicolas Le Poul, Jean-Yves Saillard, Bertrand Caro, Samia Kahlal, Pascal Le Poul, Jacqueline Vaissermann, Organométalliques et catalyse : chimie et électrochimie moléculaires (OCCEM), Université de Rennes (UR)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie du solide et inorganique moléculaire (LCSIM), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR), School of Chemistry, University of Exeter, Laboratoire de Chimie des Métaux de Transition, Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES), Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Université de Rennes 1 (UR1), and Université de Rennes (UNIV-RENNES)

Subjects
010405 organic chemistry, Transition metal carbene complex, Organic Chemistry, 010402 general chemistry, Photochemistry, Condensation reaction, 01 natural sciences, Biochemistry, Medicinal chemistry, Nmr data, 0104 chemical sciences, chemistry.chemical_compound, Deprotonation, chemistry, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Drug Discovery, Reactivity (chemistry), [CHIM.COOR]Chemical Sciences/Coordination chemistry, Single crystal, Carbene, Carbanion
Abstract

International audience; The condensation reaction between gamma-unsubstituted pyrylium salts and carbanions of Fischer-type carbene complexes allowed the synthesis of new gamma-methylenepyran carbene complexes. NMR data, single crystal X-ray analysis, and DFT calculations suggest that these complexes have a partial pyrylium character due to the pi electron-accepting ability of the carbenic fragment and to the electron-releasing properties of the methylenepyran part. (C) 2002 Elsevier Science Ltd. All rights reserved.

Published
2002
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29. Assignment of heme methyl 1H-NMR resonances of high-spin and low-spin ferric complexes of cytochrome P450cam using one-dimensional and two-dimensional paramagnetic signals enhancement (PASE) magnetization transfer experiments

Author

Rondeau-Mouro, Corinne, Bondon, Arnaud, Jung, Christiane, De Certaines, Jacques, Simonneaux, Gérard, Université de Rennes (UR), Organométalliques et catalyse : chimie et électrochimie moléculaires (OCCEM), Université de Rennes (UR)-Centre National de la Recherche Scientifique (CNRS), Max Delbrück Center for Molecular Medicine [Berlin] (MDC), Helmholtz-Gemeinschaft = Helmholtz Association, Laboratoire de résonance magnétique en biologie et en médecine, Université de Rennes (UR)-IFR91, Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES), Centre National de la Recherche Scientifique (CNRS)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES), and Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-IFR91

Subjects
[CHIM]Chemical Sciences, ComputingMilieux_MISCELLANEOUS
Abstract

International audience

Published
2000
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30. PASE (PAramagneticSignalsEnhancement): A New Method for NMR Study of Paramagnetic Proteins

Author

Arnaud Bondon, Corinne Mouro, Organométalliques et catalyse : chimie et électrochimie moléculaires (OCCEM), Université de Rennes (UR)-Centre National de la Recherche Scientifique (CNRS), Université de Rennes (UR), Centre National de la Recherche Scientifique (CNRS)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES), Université de Rennes 1 (UR1), and Université de Rennes (UNIV-RENNES)

Subjects
Nuclear and High Energy Physics, Protein Conformation, Biophysics, Analytical chemistry, Heme, 010402 general chemistry, 01 natural sciences, Biochemistry, Spectral line, Homonuclear molecule, chemistry.chemical_compound, Paramagnetism, Animals, [CHIM]Chemical Sciences, Spectroscopy, Nuclear Magnetic Resonance, Biomolecular, ComputingMilieux_MISCELLANEOUS, Myoglobin, 010405 organic chemistry, Whales, Proteins, Catalase, Condensed Matter Physics, 0104 chemical sciences, NMR spectra database, Liver, chemistry, Diamagnetism, Cattle, Two-dimensional nuclear magnetic resonance spectroscopy, Hydrogen
Abstract

A new method for NMR spectra acquisition of paramagnetic proteins is described, based on the simple use of homonuclear broadband decoupling of the diamagnetic region. Several advantages are associated with this method which was applied to one-dimensional spectra, to 1D NOE-difference spectroscopy, and to 2D NOESY. The main advantage is a very flat baseline obtained using the PASE ( pa ramagnetic s ignals e nhancement) method. Furthermore, the bulky region of the diamagnetic protons being suppressed, clean NOE-difference spectra can be acquired as well as improved 2D NOESY maps. Applications on 1D 1 H spectrum of bovine liver catalase (MW 230,000), and 1D and 2D on the high-spin form of the myoglobin, used as a model protein, are presented.

Published
1998
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31. 1H-NMR study of diamagnetic cytochrome P450cam: assignment of heme resonances and substrate dependance of one cysteinate beta proton

Author

Arnaud Bondon, Christiane Jung, Corinne Mouro, G Simonneaux, Université de Rennes (UR), Organométalliques et catalyse : chimie et électrochimie moléculaires (OCCEM), Université de Rennes (UR)-Centre National de la Recherche Scientifique (CNRS), Max Delbrück Center for Molecular Medicine [Berlin] (MDC), Helmholtz-Gemeinschaft = Helmholtz Association, Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES), Centre National de la Recherche Scientifique (CNRS)-Université de Rennes 1 (UR1), and Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)

Subjects
Models, Molecular, Magnetic Resonance Spectroscopy, Proton, Cytochrome, Camphor 5-Monooxygenase, Protein Conformation, Iron, Biophysics, Cytochrome P450, Heme, Biochemistry, Substrate Specificity, 03 medical and health sciences, chemistry.chemical_compound, Magnetics, Nuclear magnetic resonance, Structural Biology, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Genetics, Cysteine, Molecular Biology, ComputingMilieux_MISCELLANEOUS, 030304 developmental biology, 0303 health sciences, Carbon Monoxide, Binding Sites, biology, Ligand, Chemical shift, 030302 biochemistry & molecular biology, 1H-NMR, Resonance, Cell Biology, Nuclear magnetic resonance spectroscopy, Recombinant Proteins, chemistry, biology.protein, Proton NMR, Substrate interaction, Oxidation-Reduction, Hydrogen
Abstract

The 1H-NMR study of diamagnetic cytochrome P450cam FeIICO has been performed for the first time. Chemical shifts of the cysteinate fifth ligand protons and of several heme protons have been assigned through 1- and 2-dimensional spectra at 500 MHz. A substrate dependance has been observed for the resonance of the cysteinate proton detected in the high-field region.

Published
1997
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32. Comparative Fourier Transform Infrared Studies of the Secondary Structure and the CO Heme Ligand Environment in Cytochrome P-450cam and Cytochrome P-420cam †

Author

and Arnaud Bondon, Corinne Mouro, Christiane Jung, Gérard Simonneaux, Université de Rennes (UR), Max Delbrück Center for Molecular Medicine [Berlin] (MDC), Helmholtz-Gemeinschaft = Helmholtz Association, Organométalliques et catalyse : chimie et électrochimie moléculaires (OCCEM), Université de Rennes (UR)-Centre National de la Recherche Scientifique (CNRS), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES), Centre National de la Recherche Scientifique (CNRS)-Université de Rennes 1 (UR1), and Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)

Subjects
Protein Folding, Cytochrome, Camphor 5-Monooxygenase, Infrared, Analytical chemistry, Infrared spectroscopy, Heme, 010402 general chemistry, Ligands, 01 natural sciences, Biochemistry, Protein Structure, Secondary, Heating, 03 medical and health sciences, symbols.namesake, chemistry.chemical_compound, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Spectroscopy, Fourier Transform Infrared, Fourier transform infrared spectroscopy, Protein secondary structure, ComputingMilieux_MISCELLANEOUS, 030304 developmental biology, 0303 health sciences, Carbon Monoxide, Binding Sites, biology, Chemistry, Ligand, 0104 chemical sciences, Crystallography, Fourier transform, 13. Climate action, biology.protein, symbols, Thiocyanates
Abstract

For the first time, Fourier transform infrared spectroscopy has been applied to cytochrome P-450 to analyze the protein secondary structure. From Fourier self-deconvolution and fitting the infrared spectra in the amide I' region (1600-1700 cm-1), we estimate 44% alpha-helix, 31% beta-sheet, and 18% turns for substrate-free cytochrome P-450cam. In the presence of camphor, 54% alpha-helix and 310-helix, 21% beta-sheet, and 21% turns are obtained which agree with the crystallographic data of 53% alpha-helix, 19% beta-sheet, and 16% turns [Poulos, T. L., Finzel, B. C.,Howard, A. J. (1987) J. Mol. Biol. 195, 687-700]. Cytochrome P-420cam is produced from substrate-free cytochrome P-450cam in two ways: (i) by temperature elevation up to 60 degrees C and (ii) by exposure to KSCN up to 1.5 M. The secondary structure composition is determined for each temperature and KSCN concentration and compared with the changes observed in the iron ligand CO stretch vibration bands appearing between 1900 and 2000 cm-1. Thermally induced cytochrome P-420 has an alpha-helix content of 19%, a beta-sheet content of 53%, 14% turns, and 5% antiparallel beta-sheets from intermolecular hydrogen bonds within protein aggregates. The formation of cytochrome P-420 as a function of the KSCN concentration indicates two types of cytochrome P-420. Up to 1 M KSCN, the induced cytochrome P-420 displays only little modification of the secondary structure, whereas at 1.5 M KSCN, larger changes are observed, resulting in 85% cytochrome P-420 without protein precipitation and containing 30% alpha-helix, 48% beta-sheet, and 17% turns. Infrared spectra in the iron ligand CO stretch region show several subconformers for cytochrome P-420. During the cytochrome P-420 formation, the CO stretch modes are shifted to higher frequencies by 3-11 cm-1, with a main feature at about 1964 cm-1, compared to those of substrate-free cytochrome P-450cam-CO.

Published
1997
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33. Encapsulation of Pd(OAc)2 catalyst in an ionic liquid phase confined in silica gels. Application to Heck–Mizoroki reaction

Author

Olivier Lavastre, Sabrina Volland, Thomas Regnier, Marina Gruit, André Vioux, Lydie Viau, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Organométalliques et catalyse : chimie et électrochimie moléculaires (OCCEM), Université de Rennes (UR)-Centre National de la Recherche Scientifique (CNRS), Chimie moléculaire et organisation du solide (CMOS), Université Montpellier 2 - Sciences et Techniques (UM2)-Centre National de la Recherche Scientifique (CNRS), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Centre National de la Recherche Scientifique (CNRS)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES), Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes-Centre National de la Recherche Scientifique (CNRS), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Centre National de la Recherche Scientifique (CNRS), and Centre National de la Recherche Scientifique (CNRS)-Université Montpellier 2 - Sciences et Techniques (UM2)

Subjects
010405 organic chemistry, Inorganic chemistry, Significant difference, chemistry.chemical_element, [CHIM.MATE]Chemical Sciences/Material chemistry, General Chemistry, 010402 general chemistry, 01 natural sciences, Catalysis, Coupling reaction, 0104 chemical sciences, Reaction rate, chemistry.chemical_compound, chemistry, Homogeneous, Ionic liquid, Materials Chemistry, Leaching (metallurgy), Palladium
Abstract

International audience; Ionogels encapsulating Pd(OAc)2 were successfully used as catalysts in Heck–Mizoroki coupling reactions. Reaction rates were compared to homogeneous systems showing no significant difference. Leaching tests showed that catalysis actually took place in the ionic liquid phase confined within the silica matrix. The absence of leaching of palladium, the trapping of salt by-product in ionogels and the ability to produce convenient ready-to-use catalyst doses open interesting potential applications.

Published
2009
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