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1. Structure and electrochromism of two-dimensional octahedral molecular sieve h’-WO3

Author

Julie Besnardiere, Binghua Ma, Almudena Torres-Pardo, Gilles Wallez, Houria Kabbour, José M. González-Calbet, Hans Jürgen Von Bardeleben, Benoit Fleury, Valérie Buissette, Clément Sanchez, Thierry Le Mercier, Sophie Cassaignon, and David Portehault

Subjects
Science
Abstract

Thanks to their versatile redox behaviors, octahedral molecular sieves show promise in a range of electrochemical applications. Here the authors report a hexagonal polymorph of tungsten trioxide, an octahedral molecular sieve that exhibits fast proton (de)insertion for electrochromic devices.

Published
2019
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2. Off-label baclofen prescribing practices among French alcohol specialists: results of a national online survey.

Author

Benjamin Rolland, François Paille, Benoit Fleury, Olivier Cottencin, Amine Benyamina, and Henri-Jean Aubin

Subjects
Medicine, Science
Abstract

ObjectiveTo evaluate, among alcohol specialists belonging to the Société Française d'Alcoologie (SFA), i.e., the French Alcohol Society, the proportion of physicians who prescribed off-label baclofen for alcohol use disorders (AUDs). The secondary objective was to depict the features of individual prescribing and monitoring practices.MethodsOn-line survey among 484 French alcohol specialists. Physicians were asked whether they prescribed baclofen for AUDs. If they did not, the reasons for this choice were investigated. If they did, the features of the physician's prescribing practice were explored, including the number of patients treated, the mean and maximum doses, the monitoring precautions and the pharmacovigilance reporting. Participants were also asked about their empirical findings on HDB's efficacy and safety.ResultsIn total, 302 physicians (response rate of 62.4%) participated in the survey. Data from 296 participants were analysed, representing 59.4% of all active prescribing physicians belonging to the SFA. HDB use was declared by 74.6% of participants (mean dose 109.5 ± 43.6 mg/d; maximum dose 188 ± 93.3 mg/d). However, 79.2% of prescribers had treated less than 30 patients, and 67.8% used HDB as a second-line medication. Although HDB was perceived as more efficacious than approved drugs by 54.3% of prescribers, it was also declared less safe by 62.8%. Nonetheless, 79.7% of prescribers had never filed any pharmacovigilance report. Non-prescribers (25.6%) were primarily deterred by the current lack of scientific data and official regulation.ConclusionA majority of French alcohol specialists reported using HDB, although often on a limited number of their patients. HDB was considered efficacious but also potentially hazardous. Despite this, physicians reported minimal safety data to the health security system. While French health authorities are planning to draft a specific regulatory measure for framing off-label HDB prescribing practices, the sustained education of prescribers on spontaneous pharmacovigilance reporting should be enhanced.

Published
2014
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4. Co-existence of ferro- and antiferromagnetic interactions in a hexanuclear mixed-valence CoIII2MnII2MnIV2 cluster sustained by a multidentate Schiff base ligand

Author

Oleh Stetsiuk, Vladimir N. Kokozay, Miguel Julve, Joan Cano, Benoit Fleury, Narcis Avarvari, Abdelkrim El-Ghayoury, Svitlana R. Petrusenko, Francesc Lloret, Valentyn Synytsia, MOLTECH-Anjou, Université d'Angers (UA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Instituto de Ciencia Molecular (ICMol), Universitat de València (UV), Departament de Química Inorgànica,Instituto de Ciencia Molecular (ICMOL), Institut Parisien de Chimie Moléculaire (IPCM), Chimie Moléculaire de Paris Centre (FR 2769), Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), and Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Denticity, Schiff base, Valence (chemistry), Materials science, Spin states, 010405 organic chemistry, Metal ions in aqueous solution, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Inorganic Chemistry, chemistry.chemical_compound, Crystallography, chemistry, Oxidation state, [CHIM]Chemical Sciences, Antiferromagnetism, [CHIM.COOR]Chemical Sciences/Coordination chemistry, ComputingMilieux_MISCELLANEOUS, Monoclinic crystal system
Abstract

The successful utilization of the “direct synthesis” approach yielded the unprecedented hexanuclear complex of formula [Co2MnII2MnIV2(L1)4Cl2(μ3-O)2(dmf)4]·2dmf (1) (H3L is the Schiff base derived from the condensation of salicylaldehyde and 3-aminopropane-1,2-diol). Single crystal X-ray analysis revealed that 1 crystallizes in the monoclinic system P21/c and it contains a rare mixed-valence {CoIII2MnII2MnIV2(μ2-O)8(μ3-O)2} core where all metal ions are linked through the phenolato and alkoxo groups of the L3− ligand. Besides the charge balance resulting from the X-ray structure, the oxidation state of the metal ions has been confirmed by XPS spectroscopy. Cryomagnetic studies indicate the coexistence of ferro- (MnIV–MnII, J2 = +1.10(3) cm−1, J3 = +2.19(3) cm−1; MnII–MnII, j = +0.283(3) cm−1) and antiferromagnetic interactions (MnIV–MnIV, J1 = −17.31(4) cm−1), with the six-coordinate CoIII ions being diamagnetic. DFT type calculations were carried out to substantiate these values. The energy diagram for the different spin states using the best-fit parameters shows the occurrence of six low-lying spin states (S = 0–5) which are close in energy but clearly separated from the remaining ones, with the ground spin state being S = 5. Complex 1 is found to be the first example where weak ferromagnetic exchange between MnII ions through the long –O–MnIV–O– pathway takes place.

Published
2019
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5. Structure and electrochromism of two-dimensional octahedral molecular sieve h’-WO3

Author

José M. González-Calbet, Thierry Le Mercier, Houria Kabbour, Clément Sanchez, Benoit Fleury, Hans Jürgen von Bardeleben, Gilles Wallez, Sophie Cassaignon, Binghua Ma, Valérie Buissette, Julie Besnardiere, David Portehault, Almudena Torres-Pardo, Chaire Chimie des matériaux hybrides, Laboratoire de Chimie de la Matière Condensée de Paris (LCMCP), Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Departamento de Química Inorgánica, Universidad Complutense de Madrid = Complutense University of Madrid [Madrid] (UCM), Institut de Recherche de Chimie Paris (IRCP), Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), 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)-Ministère de la Culture (MC), Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Institut des Nanosciences de Paris (INSP), Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Institut Parisien de Chimie Moléculaire (IPCM), Chimie Moléculaire de Paris Centre (FR 2769), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Centre de Recherches d'Aubervilliers, RHODIA, Université de Bordeaux (UB), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ministère de la Culture (MC), Centrale Lille Institut (CLIL)-Université d'Artois (UA)-Centrale Lille-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Lille, Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), and Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)

Subjects
0301 basic medicine, Solid-state chemistry, Nanostructure, Materials science, Science, General Physics and Astronomy, 02 engineering and technology, Electrochromic devices, General Biochemistry, Genetics and Molecular Biology, Soft chemistry, 03 medical and health sciences, Electrochemistry, lcsh:Science, Multidisciplinary, Valence (chemistry), Nanoscale materials, General Chemistry, Microporous material, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, Electrochemical energy conversion, 030104 developmental biology, Chemical engineering, Electrochromism, lcsh:Q, Materials chemistry, 0210 nano-technology
Abstract

Octahedral molecular sieves (OMS) are built of transition metal-oxygen octahedra that delimit sub-nanoscale cavities. Compared to other microporous solids, OMS exhibit larger versatility in properties, provided by various redox states and magnetic behaviors of transition metals. Hence, OMS offer opportunities in electrochemical energy harnessing devices, including batteries, electrochemical capacitors and electrochromic systems, provided two conditions are met: fast exchange of ions in the micropores and stability upon exchange. Here we unveil a novel OMS hexagonal polymorph of tungsten oxide called h’-WO3, built of (WO6)6 tunnel cavities. h’-WO3 is prepared by a one-step soft chemistry aqueous route leading to the hydrogen bronze h’-H0.07WO3. Gentle heating results in h’-WO3 with framework retention. The material exhibits an unusual combination of 1-dimensional crystal structure and 2-dimensional nanostructure that enhances and fastens proton (de)insertion for stable electrochromic devices. This discovery paves the way to a new family of mixed valence functional materials with tunable behaviors.

Published
2019
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6. Structure and electrochromism of two-dimensional octahedral molecular sieve h'-WO

Author

Julie, Besnardiere, Binghua, Ma, Almudena, Torres-Pardo, Gilles, Wallez, Houria, Kabbour, José M, González-Calbet, Hans Jürgen, Von Bardeleben, Benoit, Fleury, Valérie, Buissette, Clément, Sanchez, Thierry, Le Mercier, Sophie, Cassaignon, and David, Portehault

Subjects
Article
Abstract

Octahedral molecular sieves (OMS) are built of transition metal-oxygen octahedra that delimit sub-nanoscale cavities. Compared to other microporous solids, OMS exhibit larger versatility in properties, provided by various redox states and magnetic behaviors of transition metals. Hence, OMS offer opportunities in electrochemical energy harnessing devices, including batteries, electrochemical capacitors and electrochromic systems, provided two conditions are met: fast exchange of ions in the micropores and stability upon exchange. Here we unveil a novel OMS hexagonal polymorph of tungsten oxide called h’-WO3, built of (WO6)6 tunnel cavities. h’-WO3 is prepared by a one-step soft chemistry aqueous route leading to the hydrogen bronze h’-H0.07WO3. Gentle heating results in h’-WO3 with framework retention. The material exhibits an unusual combination of 1-dimensional crystal structure and 2-dimensional nanostructure that enhances and fastens proton (de)insertion for stable electrochromic devices. This discovery paves the way to a new family of mixed valence functional materials with tunable behaviors., Thanks to their versatile redox behaviors, octahedral molecular sieves show promise in a range of electrochemical applications. Here the authors report a hexagonal polymorph of tungsten trioxide, an octahedral molecular sieve that exhibits fast proton (de)insertion for electrochromic devices.

Published
2018

7. High-resolution scanning tunneling and atomic force microscopy of stereochemically resolved dibenzo[a,h]thianthrene molecules

Author

Coral Herranz-Lancho, Mario Ruben, Judith Niedenführ, Benoit Fleury, Niko Pavliček, Jascha Repp, and Mathias Neu

Subjects
Electron density, Chemistry, Charge density, Condensed Matter Physics, Molecular physics, Electronic, Optical and Magnetic Materials, chemistry.chemical_compound, Scanning probe microscopy, Chemical bond, Computational chemistry, Molecule, Density functional theory, Physics::Chemical Physics, Thianthrene, Quantum tunnelling
Abstract

Recently, we reported on the bistable configurational switching of dibenzo[a,h]thianthrene (DBTH) molecules adsorbed on NaCl using combined low-temperature scanning tunneling and atomic force microscopy (STM/AFM). Here, we discuss the intra-molecular contrast in AFM images of the molecules as a function of the tip–molecule distance. Our experiments show that ridges in the frequency shift do not necessarily correlate with chemical bonds in this case of a non-planar molecule. To explain this finding we compare images acquired at different tip–molecule distances to the calculated electron density of the molecules obtained from density functional theory calculations (DFT). In addition, we analyze the probability of finding different configurations after adsorption onto the surface.

Published
2013
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8. Enhancing the magnetic anisotropy of maghemite nanoparticles via the surface coordination of molecular complexes

Author

Thomas Georgelin, Aude Michel, Marie-Anne Arrio, Edwige Otero, Jean-Marc Greneche, Vincent Dupuis, Fadi Choueikani, Philippe Ohresser, Jérôme Fresnais, Nader Yaacoub, Yoann Prado, Christophe Cartier-dit-Moulin, Benoit Fleury, Philippe Sainctavit, Niéli Daffé, Laurent Lisnard, PHysicochimie des Electrolytes et Nanosystèmes InterfaciauX (PHENIX), Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Institut de minéralogie, de physique des matériaux et de cosmochimie (IMPMC), Muséum national d'Histoire naturelle (MNHN)-Institut de recherche pour le développement [IRD] : UR206-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Synchrotron SOLEIL (SSOLEIL), Centre National de la Recherche Scientifique (CNRS), Laboratoire de Réactivité de Surface (LRS), Institut des Molécules et Matériaux du Mans (IMMM), Le Mans Université (UM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut Parisien de Chimie Moléculaire (IPCM), Chimie Moléculaire de Paris Centre (FR 2769), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), LABEX Matisse and MiChem (ANR-11- IDEX-0004-02), Labex Matisse, ANR-11-IDEX-0004,SUPER,Sorbonne Universités à Paris pour l'Enseignement et la Recherche(2011), Université Pierre et Marie Curie - Paris 6 (UPMC)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI 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), Institut de minéralogie et de physique des milieux condensés (IMPMC), Université Pierre et Marie Curie - Paris 6 (UPMC)-IPG PARIS-Université Paris Diderot - Paris 7 (UPD7)-Centre National de la Recherche Scientifique (CNRS), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), Université Pierre et Marie Curie - Paris 6 (UPMC)-ESPCI ParisTech-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC), Le Mans Université (UM)-Centre National de la Recherche Scientifique (CNRS), and ANR-11-IDEX-0004-02/10-LABX-0067,MATISSE,MATerials, InterfaceS, Surfaces, Environment(2011)

Subjects
[PHYS]Physics [physics], Multidisciplinary, Materials science, General Physics and Astronomy, Nanoparticle, Maghemite, General Chemistry, Coercivity, engineering.material, General Biochemistry, Genetics and Molecular Biology, Article, Characterization (materials science), Magnetic anisotropy, Nuclear magnetic resonance, Chemical engineering, engineering, Molecule, [CHIM]Chemical Sciences, Anisotropy, Order of magnitude
Abstract

Superparamagnetic nanoparticles are promising objects for data storage or medical applications. In the smallest—and more attractive—systems, the properties are governed by the magnetic anisotropy. Here we report a molecule-based synthetic strategy to enhance this anisotropy in sub-10-nm nanoparticles. It consists of the fabrication of composite materials where anisotropic molecular complexes are coordinated to the surface of the nanoparticles. Reacting 5 nm γ-Fe2O3 nanoparticles with the [CoII(TPMA)Cl2] complex (TPMA: tris(2-pyridylmethyl)amine) leads to the desired composite materials and the characterization of the functionalized nanoparticles evidences the successful coordination—without nanoparticle aggregation and without complex dissociation—of the molecular complexes to the nanoparticles surface. Magnetic measurements indicate the significant enhancement of the anisotropy in the final objects. Indeed, the functionalized nanoparticles show a threefold increase of the blocking temperature and a coercive field increased by one order of magnitude., The enhancement of the magnetic anisotropy of superparamagnetic nanoparticles may increase their functionality. Here, the authors report that the functionalization of maghemite nanoparticles with cobalt(II) complexes enhances their magnetic anisotropy, and subsequently blocking temperature and coercive field.

Published
2015
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10. Soft Magnets from the Self-Organization of Magnetic Nanoparticles in Twisted Liquid Crystals

Author

Bennie ten Haken, Nathalie Katsonis, Sarah Jane Asshoff, Benoit Fleury, Kirsten M. Pondman, Benjamin Matt, University of Twente, Equipe de Recherche en Matériaux Moléculaires et Spectroscopies (ERMMES), Institut Parisien de Chimie Moléculaire (IPCM), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), University of Twente [Netherlands], Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), Faculty of Science and Technology, Biomolecular Nanotechnology, and Magnetic Detection and Imaging

Subjects
Materials science, Physics::Optics, Nanoparticle, Nanotechnology, 02 engineering and technology, 010402 general chemistry, Smart material, 01 natural sciences, Catalysis, Magnetics, Magnetization, Liquid crystal, [CHIM]Chemical Sciences, Magnetite Nanoparticles, ComputingMilieux_MISCELLANEOUS, Temperature, General Medicine, General Chemistry, Coercivity, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Liquid Crystals, Magnet, Anisotropy, Magnetic nanoparticles, Self-assembly, 0210 nano-technology
Abstract

Organizing magnetic nanoparticles into long-range and dynamic assemblies would not only provide new insights into physical phenomena but also open opportunities for a wide spectrum of applications. In particular, a major challenge consists of the development of nanoparticle-based materials for which the remnant magnetization and coercive field can be controlled at room temperature. Our approach consists of promoting the self-organization of magnetic nanoparticles in liquid crystals (LCs). Using liquid crystals as organizing templates allows us to envision the design of tunable self-assemblies of magnetic nanoparticles, because liquid crystals are known to reorganize under a variety of external stimuli. Herein, we show that twisted liquid crystals can be used as efficient anisotropic templates for superparamagnetic nanoparticles and demonstrate the formation of hybrid soft magnets at room temperature.

Published
2014
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11. Synthesis, structure and magnetic properties of phenylhydroxamate-based coordination clusters

Author

Laurent Lisnard, Yanling Li, Rémi Tirfoin, Lise-Marie Chamoreau, Yves Journaux, Benoit Fleury, Institut Parisien de Chimie Moléculaire (IPCM), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), Equipe de Recherche en Matériaux Moléculaires et Spectroscopies (ERMMES), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Chimie Moléculaire de Paris Centre (FR 2769), Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), and Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Pivalic acid, 010405 organic chemistry, Ligand, Stereochemistry, 010402 general chemistry, 01 natural sciences, 3. Good health, 0104 chemical sciences, Inorganic Chemistry, chemistry.chemical_compound, Crystallography, chemistry, [CHIM]Chemical Sciences, [CHIM.COOR]Chemical Sciences/Coordination chemistry
Abstract

International audience; The strategic recombination of preformed coordination clusters in the presence of polymodal bridging ligands has successfully led to the characterisation of five new compounds of structural and magnetic interest. Indeed using the dinuclear complex [M2(H2O)(piv)4(Hpiv)4] (M=Co, Ni; Hpiv=pivalic acid) as starting material and reacting it with phenylhydroxamic acid (H2pha) has yielded the four tetrametallic coordination clusters [Co4(Hpha)2(piv)6(Hpiv)4] (1), [Ni4(Hpha)2(piv)6(Hpiv)2(DMF)2] (2), [Co4(Hpha)2(piv)6(EtOH)2(H2O)2] (3), [Ni4(Hpha)2(piv)6(EtOH)2(H2O)2] (4) and the hexanuclear complex [Co6(Hpha)4(piv)8(EtOH)2]·EtOH (5). All the compounds have been structurally characterised revealing a particular binding mode for the hydroxamate ligand. The study of their magnetic properties has been performed and the modelling of these properties has been done using the appropriate hamiltonians for each compound. The experimental data and their modellings show non-zero spin ground states for compounds 4 and 5.

Published
2014
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12. Atomic Force Microscopy Reveals Bistable Configurations of Dibenzo[a,h]thianthrene and their Interconversion Pathway

Author

Mathias Neu, Niko Pavliček, Mario Ruben, Benoit Fleury, Coral Herranz-Lancho, Judith Niedenführ, and Jascha Repp

Subjects
Materials science, Bistability, ddc:540, General Physics and Astronomy, Nanotechnology, 68.43.Fg, law.invention, Condensed Matter::Materials Science, chemistry.chemical_compound, Adsorption, law, Physics::Atomic and Molecular Clusters, Molecule, Physics::Chemical Physics, 68.37.Ef, Thianthrene, Quantum tunnelling, ddc:530, Resolution (electron density), 530 Physik, 82.37.Gk, Molecular geometry, chemistry, Chemical physics, 540 Chemie, Scanning tunneling microscope, 68.37.Ps
Abstract

We investigated dibenzo[a,h]thianthrene molecules adsorbed on ultrathin layers of NaCl using a combined low-temperature scanning tunneling and atomic force microscope. Two stable configurations exist corresponding to different isomers of free nonplanar molecules. By means of excitations from inelastic electron tunneling we can switch between both configurations. Atomic force microscopy with submolecular resolution allows unambiguous determination of the molecular geometry, and the pathway of the interconversion of the isomers. Our investigations also shed new light on contrast mechanisms in scanning tunneling microscopy.

Published
2012
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13. Sequential Growth in Solution of NiFe Prussian Blue coordination network nanolayers on Si(100) surfaces

Author

Florence Volatron, Claire Costa-Coquelard, Frédéric Miserque, Pierre-Antoine Albouy, Serge Palacin, Pascale Jégou, Vincent Huc, Benoit Fleury, Simon Tricard, Talal Mallah, C. David, Institut de Chimie Moléculaire et des Matériaux d'Orsay (ICMMO), Université Paris-Sud - Paris 11 (UP11)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Physique des Solides (LPS), Université Paris-Sud - Paris 11 (UP11)-Centre National de la Recherche Scientifique (CNRS), ISARA-Lyon, Laboratoire d'Etude de la Corrosion Aqueuse (LECA), Service de la Corrosion et du Comportement des Matériaux dans leur Environnement (SCCME), Département de Physico-Chimie (DPC), CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Département de Physico-Chimie (DPC), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay, Laboratoire de Chimie des Surfaces et Interfaces (LCSI), Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Centre National de la Recherche Scientifique (CNRS)-Université Paris-Sud - Paris 11 (UP11), and Université Paris-Sud - Paris 11 (UP11)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)

Subjects
Coordination sphere, Analytical chemistry, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Inorganic Chemistry, chemistry.chemical_compound, X-ray photoelectron spectroscopy, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Molecule, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Thin film, Nanoscopic scale, ComputingMilieux_MISCELLANEOUS, Prussian blue, [CHIM.CATA]Chemical Sciences/Catalysis, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, 0104 chemical sciences, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Attenuated total reflection, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], Physical chemistry, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], Ferrocyanide, 0210 nano-technology
Abstract

Controlling the elaboration of Coordination Networks (CoNet) on surfaces at the nanoscale remains a challenge. One suitable technique is the Sequential Growth in Solution (SGS), which has the advantage to be simple, cheap and fast. We addressed two issues in this article: i) the controlled synthesis of ultra thin films of CoNet (thickness lower than 10 nm), and ii) the investigation of the influence of the precursors' concentration on the growth process. Si(100) was used because it is possible to prepare atomically flat Si-H surfaces, which is necessary for the growth of ultrathin films. We used, as a model system, the sequential reactions of K(4)[Fe(II)(CN)(6)] and [Ni(II)(H(2)O)(6)]Cl(2) that occur by the substitution of the water molecules in the coordination sphere of Ni(II) by the nitrogen atoms of ferrocyanide. We demonstrated that the nature of the deposited film depends mainly on the relative concentration of the anchoring sites versus the precursors' solution. Attenuated Total Reflection Fourier Transformed Infra Red (ATR-FTIR), X-ray reflectivity, X-ray Photoelectron Spectroscopy (XPS) and Atomic Force Microscopy (AFM) were used to characterize the steps of the growth process.

Published
2012
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14. Tuning the spin-transition properties of pyrene-decorated 2,6-bispyrazolylpyridine based Fe(II) complexes

Author

Mario Ruben, Benoit Fleury, Sergei Lebedkin, Manfred M. Kappes, Olaf Fuhr, Rodrigo González-Prieto, Giorgio Zoppellaro, Frank Schramm, and Rajadurai Chandrasekar

Subjects
Models, Molecular, Pyrenes, Spin states, Ligand, Pyridines, Spin transition, Stacking, Temperature, Photochemistry, Crystallography, X-Ray, Ligands, Inorganic Chemistry, chemistry.chemical_compound, Crystallography, Magnetics, chemistry, Pyridine, Luminescent Measurements, Pyrene, Single bond, Moiety, Pyrazoles, Ferrous Compounds
Abstract

Two 2,6-bispyrazolylpyridine ligands (bpp) were functionalized with pyrene moieties through linkers of different lengths. In the ligand 2,6-di(1H-pyrazol-1-yl)-4-(pyren-1-yl)pyridine (L1) the pyrene group is directly connected to the bpp moiety via a C-C single bond, while in the ligand 4-(2,6-di(1H-pyrazol-1-yl)pyridin-4-yl)benzyl-4-(pyren-1-yl)butanoate (L2) it is separated by a benzyl ester group involving a flexible butanoic chain. Subsequent complexation of Fe(II) salts revealed dramatic the influence of the nature of the pyrene substitution on the spin-transition behaviour of the resulting complexes. Thus, compound [Fe(L1)(2)](ClO(4))(2) (1) is blocked in its high spin state due to constraints caused by a strong intermolecular π-π stacking in its structure. On the other hand, the flexible chain of ligand L2 in compounds [Fe(L2)(2)](ClO(4))(2) (2) and [Fe(L2)(2)](BF(4))(2)·CH(3)CN·H(2)O (3) prevents structural constraints allowing for reversible spin transitions. Temperature-dependent studies of the photophysical properties of compound 3 do not reveal any obvious correlation between the fluorescence of the pyrene group and the spin state of the spin transition core.

Published
2011

15. Electrostatic immobilization of polyoxometallates on silicon: X-ray Photoelectron Spectroscopy and electrochemical studies

Author

Gérard Bidan, Florence Duclairoir, Martial Billon, Benoit Fleury, Aurélien Fanton, Lionel Dubois, Institut Nanosciences et Cryogénie (INAC), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA), Structures et propriétés d'architectures moléculaire (SPRAM - UMR 5819), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA)-Centre National de la Recherche Scientifique (CNRS), Reconnaissance Ionique et Chimie de Coordination (RICC), SYstèmes Moléculaires et nanoMatériaux pour l’Energie et la Santé (SYMMES), Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Laboratoire d'Electronique et des Technologies de l'Information (CEA-LETI), Université Grenoble Alpes (UGA)-Direction de Recherche Technologique (CEA) (DRT (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), Equipe de Recherche en Matériaux Moléculaires et Spectroscopies (ERMMES), Institut Parisien de Chimie Moléculaire (IPCM), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Chimie pour la Reconnaissance et l’Etude d’Assemblages Biologiques (CREAB), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives - Laboratoire d'Electronique et de Technologie de l'Information (CEA-LETI), Direction de Recherche Technologique (CEA) (DRT (CEA)), Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie du CNRS (INC)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Silicon, Chemistry, Inorganic chemistry, Metals and Alloys, chemistry.chemical_element, Protonation, 02 engineering and technology, Surfaces and Interfaces, Tungsten, 010402 general chemistry, 021001 nanoscience & nanotechnology, Electrochemistry, Electrostatics, 01 natural sciences, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, X-ray photoelectron spectroscopy, Covalent bond, Materials Chemistry, [CHIM]Chemical Sciences, Cyclic voltammetry, 0210 nano-technology, ComputingMilieux_MISCELLANEOUS
Abstract

Keggin-type dodecatungstosilicates polyoxometallates (POMs) ([SiW 12 O 40 ] 4− ) were immobilized in a straightforward manner by electrostatic interactions on ammonium layers covalently grafted on silicon. This method does not require any POM modification synthetical steps. The presence of [SiW 12 O 40 ] 4− on the surface is demonstrated by X-ray Photoelectron Spectroscopy from a specific modification of the tungsten 4f 7/2 signal. Moreover the surface coverage of [SiW 12 O 40 ] 4− has been improved by 35% upon changing the nature of the anchoring ammonium groups from protonated to methylated amino groups. The organic–inorganic composite films have also been characterized by cyclic voltammetry showing that POMs have a specific behavior on silicon surfaces. In addition the use of a polyallylamine capping layer proved to stabilize efficiently the POM electrochemical response.

Published
2011
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16. Growth and density control of nanometric nickel–iron cyanide-bridged objects on functionalized Si(100) surface

Author

François Brisset, Vincent Huc, C. David, Benoit Fleury, Claire Costa-Coquelard, Florence Volatron, Talal Mallah, Pascale Jégou, Serge Palacin, Sandra Mazerat, Simon Tricard, Frédéric Miserque, Laboratoire de physique et chimie des nano-objets (LPCNO), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie de Toulouse (ICT-FR 2599), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de photonique et de nanostructures (LPN), Centre National de la Recherche Scientifique (CNRS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Laboratoire de Chimie des Surfaces et Interfaces (LCSI), Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Université Toulouse III - Paul Sabatier (UT3), and Université de Toulouse (UT)-Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Surface (mathematics), Materials science, Nucleation, chemistry.chemical_element, Nanotechnology, 010402 general chemistry, 01 natural sciences, Catalysis, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Materials Chemistry, Coordination network, [CHIM.COOR]Chemical Sciences/Coordination chemistry, 010405 organic chemistry, Metals and Alloys, General Chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, [CHIM.MATE]Chemical Sciences/Material chemistry, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Nickel, [CHIM.POLY]Chemical Sciences/Polymers, Chemical engineering, chemistry, Scientific method, Ceramics and Composites, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], Iron cyanide, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph]
Abstract

International audience; Isolated nanometric objects of the nickel–iron cyanide-bridged coordination network are obtained by a sequential growth on “molecular seeds” anchored on Si(100) surfaces. Control of the density and the size of the nano-objects is achieved by imposing a growth process without side nucleation.

Published
2010
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17. Orientation of Mn12 molecular nanomagnets in self-assembled monolayers

Author

Laure Catala, C. David, Vincent Huc, Laurent Baraton, Talal Mallah, Serge Palacin, Benoit Fleury, Pascale Jégou, Institut de Chimie Moléculaire et des Matériaux d'Orsay (ICMMO), Université Paris-Sud - Paris 11 (UP11)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie des Surfaces et Interfaces (LCSI), Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Laboratoire de photonique et de nanostructures (LPN), Centre National de la Recherche Scientifique (CNRS), and Université Paris-Sud - Paris 11 (UP11)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)

Subjects
Materials science, Coordination sphere, Molecular nanomagnets, Self-assembled monolayer, 02 engineering and technology, General Chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, Orientation (graph theory), 010402 general chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, Grafting, 01 natural sciences, 0104 chemical sciences, chemistry.chemical_compound, Crystallography, chemistry, General Materials Science, Carboxylate, 0210 nano-technology, Selectivity
Abstract

International audience; The oriented grafting of the Mn12-carboxylate molecular nanomagnets has been achieved on semi-conducting flat Si(100) functionalized surfaces due to the bonding selectivity between axial and equatorial carboxylate groups present in the coordination sphere of the Mn12 complexes.

Published
2009
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18. Porphyrin anchoring on Si(100) using a β-pyrrolic position

Author

Lionel Dubois, Hui Liu, Florence Duclairoir, Jean-Claude Marchon, Yves Chenavier, Benoit Fleury, Laboratoire de Modélisation et de Management des Organisations (LM²O), Ecole Centrale de Lille, Reconnaissance Ionique et Chimie de Coordination (RICC), SYstèmes Moléculaires et nanoMatériaux pour l’Energie et la Santé (SYMMES), Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Institut Nanosciences et Cryogénie (INAC), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA), Conception d’Architectures Moléculaires et Processus Electroniques (CAMPE), Centrale Lille, Institut de Chimie du CNRS (INC)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS), Service de Chimie Inorganique et Biologique (SCIB - UMR E3), Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS), Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Centre National de la Recherche Scientifique (CNRS), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])

Subjects
chemistry.chemical_classification, Silicon, Hydrosilylation, Stereochemistry, chemistry.chemical_element, Alkyne, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, Triple bond, 01 natural sciences, Porphyrin, Cycloaddition, 0104 chemical sciences, Inorganic Chemistry, chemistry.chemical_compound, Crystallography, chemistry, [CHIM]Chemical Sciences, 0210 nano-technology, Bifunctional, Linker, ComputingMilieux_MISCELLANEOUS
Abstract

Nickel(II) beta-azido-meso-tetraphenylporphyrin was successfully anchored on silicon using a bifunctional linker that bears two terminal alkyne functions by the sequence (i) hydrosilylation of a C[triple bond]C triple bond of the linker by surface Si-H groups and (ii) 1,3-Huisgen cycloaddition between the alkyne-terminated silicon surface and the azidoporphyrin derivative.

Published
2009
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19. Grafting a monolayer of superparamagnetic cyanide-bridged coordination nanoparticles on Si(100)

Author

Florence Volatron, Guillaume Rogez, C. David, Serge Palacin, Vincent Huc, Eric Rivière, Benoit Fleury, Laure Catala, Talal Mallah, Daniela Brinzei, Frédéric Miserque, Laurent Baraton, Institut de Chimie Moléculaire et des Matériaux d'Orsay (ICMMO), Université Paris-Sud - Paris 11 (UP11)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de photonique et de nanostructures (LPN), Centre National de la Recherche Scientifique (CNRS), Laboratoire d'Etude de la Corrosion Aqueuse (LECA), Service de la Corrosion et du Comportement des Matériaux dans leur Environnement (SCCME), Département de Physico-Chimie (DPC), CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-CEA-Direction des Energies (ex-Direction de l'Energie Nucléaire) (CEA-DES (ex-DEN)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Département de Physico-Chimie (DPC), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay, Institut de Physique et Chimie des Matériaux de Strasbourg (IPCMS), Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie des Surfaces et Interfaces (LCSI), Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Université Paris-Sud - Paris 11 (UP11)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Université de Strasbourg (UNISTRA)-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, and Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)

Subjects
Chemistry, Cyanide, Substrate (chemistry), Nanoparticle, Nanotechnology, 02 engineering and technology, [CHIM.MATE]Chemical Sciences/Material chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, Grafting, equipment and supplies, 01 natural sciences, 0104 chemical sciences, Inorganic Chemistry, chemistry.chemical_compound, surgical procedures, operative, Chemical engineering, Monolayer, Physical and Theoretical Chemistry, 0210 nano-technology, human activities, Superparamagnetism
Abstract

International audience; The grafting of a monolayer of 6 nm superparamagnetic cyanide-bridged CsNiCr nanoparticles was achieved on a Ni(II)-functionalized Si(100) substrate; magnetic studies reveals that the grafted nanoparticles are nearly magnetically isolated within the monolayer

Published
2008
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20. Bistable molecules development and Si surface grafting: two chemical tools used for the fabrication of hybrid molecule/Si CMOS component

Author

Pascale Maldivi, Gérard Bidan, Regis Barattin, Martial Billon, K. Huang, Florence Duclairoir, Barbara De Salvo, Alexandra Fateeva, Lionel Dubois, T. Pro, Adrian Calborean, Anbarasan Kalaiselvan, Benoit Fleury, Jean-Claude Marchon, Julien Buckley, and Guillaume Delapierre

Subjects
Materials science, Fabrication, Bistability, Silicon, Capacitive sensing, Molecular electronics, chemistry.chemical_element, Bioengineering, Nanotechnology, Condensed Matter Physics, Capacitance, CMOS, chemistry, Materials Chemistry, Molecule, Electrical and Electronic Engineering
Abstract

For the past ten years, there has been considerable interest dedicated to the miniaturisation of CMOS devices. The research axes followed to obtain scalable devices are numerous as the possibilities offered by both technological (top-down) and new (bottom-up) approaches are studied. Concerning the latter approach molecular electronics is a growing field of interest. Notably, the fabrication of hybrid molecule/Si structures paves the way for development of devices with electrical performances that can be tuned thanks to the molecular properties initially targeted. Here we present the recent results obtained in the two approaches we follow in order to develop new hybrid molecule/Si memory elements. The first axis focuses on the development of specific molecules that could allow a fine tuning of the memory retention characteristic. The second axis deals with the integration of redox molecules inside capacitive cells and the study of their electrical properties. The capacitance of such components clearly shows that an effect of charge transfer is observed only when redox active molecules (porphyrins) are grafted on Si.

Published
2010
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21. A new approach to grafting a monolayer of oriented Mn12 nanomagnets on silicon

Author

Laurent Baraton, Laure Catala, Serge Palacin, Wang Zhao Zhong, Benoit Fleury, C. David, Vincent Huc, Pierre-Antoine Albouy, Pascale Jégou, Talal Mallah, Institut de Chimie Moléculaire et des Matériaux d'Orsay (ICMMO), Université Paris-Sud - Paris 11 (UP11)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Laboratoire de photonique et de nanostructures (LPN), Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie des Surfaces et Interfaces (LCSI), Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Laboratoire de Physique des Solides (LPS), Centre National de la Recherche Scientifique (CNRS)-Université Paris-Sud - Paris 11 (UP11), Université Paris-Sud - Paris 11 (UP11)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Université Paris-Sud - Paris 11 (UP11)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Materials science, Silicon, Metals and Alloys, chemistry.chemical_element, Nanotechnology, [CHIM.MATE]Chemical Sciences/Material chemistry, 02 engineering and technology, General Chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, Grafting, 01 natural sciences, Nanomagnet, Catalysis, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, chemistry, Monolayer, Materials Chemistry, Ceramics and Composites, Wafer, 0210 nano-technology
Abstract

International audience; The functionalisation of a Si(100) silicon wafer allows for the oriented grafting of a monolayer of Mn12 nanomagnets using a two-step procedure

Published
2005
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22. Tuning the spin-transition properties of pyrene-decorated 2,6-bispyrazolylpyridine based Fe(ii) complexesElectronic supplementary information (ESI) available: NMR, ESI mass and IR spectra of ligands L1and L2, and compounds 1, 2and 3. Emission spectra of 3excited at 270 nm and normalized emission intensity of polycrystalline pyrene butyric acid as a function of the temperature. X-Ray crystallographic parameters of 1. CCDC reference number 790319. For ESI and crystallographic data in CIF or other electronic format, see DOI: 10.1039/c1dt10420a

Author

Rodrigo González-Prieto, Benoit Fleury, Frank Schramm, Giorgio Zoppellaro, Rajadurai Chandrasekar, Olaf Fuhr, Sergei Lebedkin, Manfred Kappes, and Mario Ruben

Subjects
*PYRENE, *IRON compounds, *LIGANDS (Chemistry), *METAL complexes, *SUBSTITUTION reactions, *FLUORESCENCE
Abstract

Two 2,6-bispyrazolylpyridine ligands (bpp) were functionalized with pyrene moieties through linkers of different lengths. In the ligand 2,6-di(1H-pyrazol-1-yl)-4-(pyren-1-yl)pyridine (L1) the pyrene group is directly connected to the bpp moiety viaa C–C single bond, while in the ligand 4-(2,6-di(1H-pyrazol-1-yl)pyridin-4-yl)benzyl-4-(pyren-1-yl)butanoate (L2) it is separated by a benzyl ester group involving a flexible butanoic chain. Subsequent complexation of Fe(ii) salts revealed dramatic the influence of the nature of the pyrene substitution on the spin-transition behaviour of the resulting complexes. Thus, compound [Fe(L1)2](ClO4)2(1) is blocked in its high spin state due to constraints caused by a strong intermolecular π–π stacking in its structure. On the other hand, the flexible chain of ligand L2in compounds [Fe(L2)2](ClO4)2(2) and [Fe(L2)2](BF4)2·CH3CN·H2O (3) prevents structural constraints allowing for reversible spin transitions. Temperature-dependent studies of the photophysical properties of compound 3do not reveal any obvious correlation between the fluorescence of the pyrene group and the spin state of the spin transition core. [ABSTRACT FROM AUTHOR]

Published
2011

23. Orientation of Mn12 molecular nanomagnets in self-assembled monolayers.

Author

Benoit Fleury, Vincent Huc, Laure Catala, Pascale Jegou, Laurent Baraton, Christophe David, Serge Palacin, and Talal Mallah

Subjects
*METAL complexes, *MANGANESE compounds, *MOLECULAR self-assembly, *MONOMOLECULAR films, *CARBOXYLIC acids, *SEMICONDUCTORS, *SILICON, *NANOSTRUCTURED materials
Abstract

The oriented grafting of the Mn12-carboxylate molecular nanomagnets has been achieved on semi-conducting flat Si(100) functionalized surfaces due to the bonding selectivity between axial and equatorial carboxylate groups present in the coordination sphere of the Mn12complexes. [ABSTRACT FROM AUTHOR]

Published
2009
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24. Les conduites d'alcoolisation : Du repérage précoce au réseau de prise en charge

Author

Benoît Fleury, Collectif John Libbey, Benoît Fleury, and Collectif John Libbey

Subjects
Alcoholism, Alcoholism--Treatment
Abstract

L'alcool est, en France, très présente dans notre vie et dans notre société. Les rapports entre les individus et l'alcool sont variés et complexes. Si sa consommation à doses faibles présente peu de risque pour la majorité des personnes, son abus, même sans dépendance, peut avoir de graves conséquences sur le comportement et la santé. Les conduites d'alcoolisation sont polymorphes : usage, mésusage, abus avec ou sans dépendance ; elles ont fait récemment l'objet de nouvelles définitions et classifications, précieuses pour les cliniciens soucieux de prévenir, dépister, orienter et/ou accompagner. La prise en charge doit être globale et s'étend souvent aux milieux familial et professionnel. Un accompagnement pluridisciplinaire et un véritable travail en réseau sont donc des conditions essentielles pour tenter de soulager ces patients. Cet ouvrage, coordonné par le Dr Benoît Fleury, intéressera les soignants : médecins, psychologues, les structures de soins (hôpitaux, cliniques, centres de postcure), les centres de cure ambulatoire en alcoologie (CCAA), les centres de soins spécialisés en toxicomanie (CSST), ainsi que l'ensemble des travailleurs sociaux.

Published
2003

25. Growth and density control of nanometric nickel–iron cyanide-bridged objects on functionalized Si(100) surfaceElectronic supplementary information (ESI) available: AFM imaging, ATR-IR and XPS spectra, synthetic procedures. See DOI: 10.1039/c003039b

Author

Simon Tricard, Benoit Fleury, Florence Volatron, Claire Costa-Coquelard, Sandra Mazerat, Vincent Huc, Christophe David, François Brisset, Frédéric Miserque, Pascale Jegou, Serge Palacin, and Talal Mallah

Subjects
*NANOSTRUCTURED materials, *TRANSITION metal compounds, *CYANIDES, *SILICON, *DENSITY, *NUCLEATION, *SURFACE chemistry
Abstract

Isolated nanometric objects of the nickel–iron cyanide-bridged coordination network are obtained by a sequential growth on “molecular seeds” anchored on Si(100) surfaces. Control of the density and the size of the nano-objects is achieved by imposing a growth process without side nucleation. [ABSTRACT FROM AUTHOR]

Published
2010
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27. Does vanadium play a role in depressive states?

Author

Claude Conri, M. Simonoff, Benoit Fleury, and François Moreau

Subjects
Adult, Male, medicine.medical_specialty, Depressive Disorder, Bipolar Disorder, business.industry, Vanadium, chemistry.chemical_element, Middle Aged, Endocrinology, Sex Factors, chemistry, Psychotic Disorders, Internal medicine, medicine, Humans, In patient, Female, business, Biological Psychiatry, Depression (differential diagnoses), Aged
Abstract

Depressive states are associated with various clinical or biochemical anomalies, some of which are considered to be signs or indicators ot depression (Extein et al. 1981: Harrison et al. 1984). Several studies have suggested that vanadium may play an important role in depresalve states by regulating the activny of the ubiquitous enzyme. Na-K-ATPasc. thereby directly affecting the activity of the membrane sodium pumps at either the peripheral level (Naylor and Smith 198 I) or the brain (Robinson 198 I ). The amount of work that has been carried out on the subject of vanadium and depressive illness has undoubtedly been limited by the major technical difficulties involved in the measurement of small concentrations of vanadium in bioloplcal media. as the values obtained are strongly dependent on the method employed. In this preliminary study. wc attempted to determine whether or not differences in serum vanadium levels could be detected in patients suffering from various forms of depression compared with normal subjects. The vanadium determinations were carried out at P. Siie Labo

Published
1986

28. Variations in serum vanadium levels during the treatment of mental depression

Author

M. Simonoff, Benoit Fleury, Claude Conri, and François Moreau

Subjects
Adult, Male, medicine.medical_specialty, Depressive Disorder, Psychotropic Drugs, Vanadium, chemistry.chemical_element, Middle Aged, chemistry, Mental depression, medicine, Humans, Female, Psychiatry, Biological Psychiatry, Aged
Published
1986

29. Hybrid semiconducting nanoplatelets : synthesis and molecule-driven assembly

Author

Flores, Yesica, Institut Parisien de Chimie Moléculaire (IPCM), Chimie Moléculaire de Paris Centre (FR 2769), Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Sorbonne Université, and Benoit Fleury

Subjects
Nanocristaux, Semiconducteurs, Nanoplatelets, Assembly, Assemblage, Hybrids, Hybrides, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Semiconductor, [CHIM.MATE]Chemical Sciences/Material chemistry, Photoluminescence, Nanocrystals, Nanoplaquettes
Abstract

This Ph.D. aimed at a better understanding of the chemical properties of cadmium selenide nanoplatelets by functionalization by paramagnetic coordination complexes. Indeed, the original optical properties of the platelets associated to the paramagnetism of transition metal complexes could lead to new magneto-optic properties. In agreement with recent literature results, this Ph.D. confirms that the planar morphology of these nano-objets induces their stacking when covered by appropriate ligands and dispersed in appropriate solvents. This thesis presents three chapters about (i) the description of the structure and the properties of CdSe nanoplatelets, (ii) a study of azobenzenedecorated nanoplatelets and (iii) the self-assembly of CdSe nanoplatelets mediated by cobalt(II) phtalocyanines to produce composite materials. This work shows that functionalizing CdSe nanoplatelets with azobenzene moieties allows their out-of-equilibrium assembly. Furthermore, two ways of assembling nanoplatelets with cobalt(II) phtalocyanines have been developed leading to composites bearing different structures. For one of these structures a circularly polarized light is emitted under magnetic field revealing a symmetry braking in the composite thanks to the cobalt complex and thus magneto-optic effects.; Ce doctorat avait pour objet l’exploration des propriétés chimiques de nanoplaquettes de séléniure de cadmium en les fonctionnalisant par des complexes paramagnétiques de coordination. En effet, l’association des propriétés magnétiques des complexes avec les propriétés optiques très originales de ces objets pourrait conduire à la découverte de nouvelles propriétés magnéto-optiques. Cette thèse, en cohérence avec des résultats récents de la littérature, a confirmé que la forme plaquettaire de ces nano-objets induisait leur empilement lorsqu’ils sont recouverts de ligands appropriés et dispersés dans des solvants adaptés. Cette thèse présente trois chapitres portant sur (i) la description des nanoplaquettes de CdSe du point de vue de leur structure et de leurs propriétés, (ii) une étude de l’assemblage des plaquettes lorsque celles-ci sont fonctionnalisées par des molécules de type azobenzène isomérisable et (iii) l’étude de l’assemblage des nanoplaquettes par l’intermédiaire de phtalocyanines de cobalt(II) conduisant à des matériaux composites. Nous avons montré que la fonctionnalisation des nanoplaquettes par des molécules d’azobenzène permettait leur assemblage hors équilibre c’est à dire sous apport continu d’énergie. Par ailleurs, deux voies d’assemblage des nanoplaquettes avec la phtalocyanine de cobalt ont été explorées. Ces deux voies permettent d’obtenir des composites de structures différentes et dans un cas il a été observé une émission de lumière polarisée circulairement sous champ magnétique. Ce résultat montre l’existence d’une rupture de symétrie dans le composite liée à la présence du complexe de cobalt et donc l’apparition de propriétés magnéto-optiques.

Published
2018

30. Nanoplaquettes semi-conductrices hybrides : synthèse et assemblage par l’intermédiaire de molecules

Author

Flores, Yesica, Institut Parisien de Chimie Moléculaire (IPCM), Chimie Moléculaire de Paris Centre (FR 2769), Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Sorbonne Université, and Benoit Fleury

Subjects
Nanocristaux, Semiconducteurs, Nanoplatelets, Assembly, Assemblage, Hybrids, Hybrides, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Semiconductor, [CHIM.MATE]Chemical Sciences/Material chemistry, Photoluminescence, Nanocrystals, Nanoplaquettes
Abstract

This Ph.D. aimed at a better understanding of the chemical properties of cadmium selenide nanoplatelets by functionalization by paramagnetic coordination complexes. Indeed, the original optical properties of the platelets associated to the paramagnetism of transition metal complexes could lead to new magneto-optic properties. In agreement with recent literature results, this Ph.D. confirms that the planar morphology of these nano-objets induces their stacking when covered by appropriate ligands and dispersed in appropriate solvents. This thesis presents three chapters about (i) the description of the structure and the properties of CdSe nanoplatelets, (ii) a study of azobenzenedecorated nanoplatelets and (iii) the self-assembly of CdSe nanoplatelets mediated by cobalt(II) phtalocyanines to produce composite materials. This work shows that functionalizing CdSe nanoplatelets with azobenzene moieties allows their out-of-equilibrium assembly. Furthermore, two ways of assembling nanoplatelets with cobalt(II) phtalocyanines have been developed leading to composites bearing different structures. For one of these structures a circularly polarized light is emitted under magnetic field revealing a symmetry braking in the composite thanks to the cobalt complex and thus magneto-optic effects.; Ce doctorat avait pour objet l’exploration des propriétés chimiques de nanoplaquettes de séléniure de cadmium en les fonctionnalisant par des complexes paramagnétiques de coordination. En effet, l’association des propriétés magnétiques des complexes avec les propriétés optiques très originales de ces objets pourrait conduire à la découverte de nouvelles propriétés magnéto-optiques. Cette thèse, en cohérence avec des résultats récents de la littérature, a confirmé que la forme plaquettaire de ces nano-objets induisait leur empilement lorsqu’ils sont recouverts de ligands appropriés et dispersés dans des solvants adaptés. Cette thèse présente trois chapitres portant sur (i) la description des nanoplaquettes de CdSe du point de vue de leur structure et de leurs propriétés, (ii) une étude de l’assemblage des plaquettes lorsque celles-ci sont fonctionnalisées par des molécules de type azobenzène isomérisable et (iii) l’étude de l’assemblage des nanoplaquettes par l’intermédiaire de phtalocyanines de cobalt(II) conduisant à des matériaux composites. Nous avons montré que la fonctionnalisation des nanoplaquettes par des molécules d’azobenzène permettait leur assemblage hors équilibre c’est à dire sous apport continu d’énergie. Par ailleurs, deux voies d’assemblage des nanoplaquettes avec la phtalocyanine de cobalt ont été explorées. Ces deux voies permettent d’obtenir des composites de structures différentes et dans un cas il a été observé une émission de lumière polarisée circulairement sous champ magnétique. Ce résultat montre l’existence d’une rupture de symétrie dans le composite liée à la présence du complexe de cobalt et donc l’apparition de propriétés magnéto-optiques.

Published
2018

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