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1. Single polyoxometalate-based nanoclusters characterized by infrared absorption nanospectroscopy

Author

Juba Salhi, Michele Mattera, Imad Arfaoui, Jan Patrick Calupitan, Sandra Alves, Claire Troufflard, Céline Paris, Guillaume Izzet, Anna Proust, David Kreher, Guilhem Simon, Alexandre Dazzi, and Florence Volatron

Subjects
Chemistry, QD1-999
Abstract

Abstract Bottom-up engineering is a very attractive field. However, the periodic organization of molecules on a solid substrate is challenging, particularly in the selection of the appropriate characterization technique which is suitable for both large area and accurate analysis at the nanoscale. Here, this study demonstrates the unambiguous identification of complex molecular layers by infrared absorption microscopy at the nanometric scale. This technique allowed for the direct observation of the presence of isolated polyoxometalate-based nanoclusters dispersed all over a substrate.

Published
2024
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2. Multifunctional Supramolecular Gels with Strong Mechanical Properties Formed by Self-Assembly of Polyoxometalate-Based Coordination Polymers

Author

Lorenzo Casimiro, Florence Volatron, Grégoire Boivin, Benjamin Abécassis, Sandra Alves, Dalil Brouri, David Montero, Jean-Michel Guigner, Lise-Marie Chamoreau, Geoffrey Gontard, David Portehault, Yanling Li, Anna Proust, Rodrigue Lescouëzec, Guylaine Ducouret, Albert Solé-Daura, Patrick Davidson, Théo Merland, and Guillaume Izzet

Subjects
Chemistry, QD1-999
Published
2024
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3. Layer‐by‐Layer Construction of Hybrid Film Based on PEI Polymer and Preyssler‐Type Polyoxometalates: Its Electrochemical and Quartz Crystal Microbalance Measurement

Author

Athira Kuruly Rajan, Indherjith Sakthinathan, Séverine Renaudineau, Anna Proust, and Timothy McCormac

Subjects
Polyoxometalate, Preyssler, Layer by Layer, Polyethyleneimine, EQCM, Industrial electrochemistry, TP250-261, Chemistry, QD1-999
Abstract

Abstract In this work, Preyssler‐type POM (NH4)14[NaP5W30O110].44H2O (NH4P5W30), has been synthesised and its electrochemical behaviour in solution was examined at the surface of glassy carbon (GC) and gold electrodes. Furthermore, multilayer assemblies of NH4P5W30 POM were constructed onto the surfaces of GCE, gold electrode, and gold quartz electrode via the electrostatic Layer‐by‐Layer (LBL) technique employing polyethyleneimine as the cationic layer and POM as an anionic layer. Cyclic voltammetry, electrochemical impedance spectroscopy (EIS), and electrochemical quartz crystal microbalance measurements (EQCM) were used to monitor the LBL assembly as the NH4P5W30 POM layer was being built. These techniques revealed significant differences in film growth. The multilayer film exhibited well‐defined redox couples associated with POM's tungsten‐oxo framework and showed surface‐confined behaviour up to 100 mVs−1 on both the GC and gold electrodes. The pH dependency and stability of the film were investigated. EIS demonstrated that when the POM layer was the outer layer, the layers were less conductive, and resistance increased as the number of layers increased. In addition, the charge transfer resistance values (Rct) for the layers were calculated. The solvation of ions into the film associated with POM redox activity was studied employing an in‐situ EQCM.

Published
2024
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4. Protective Effect of Polyoxometalates in {Mo132}/Maghemite Binary Superlattices Under Annealing

Author

Romain Breitwieser, Adrien Garnier, Thomas Auvray, Anh-Tu Ngo, Benoit Baptiste, Nicolas Menguy, Anna Proust, Christophe Petit, Florence Volatron, and Caroline Salzemann

Subjects
binary superlattices, maghemite, polyoxometalates, magnetism, annealing, Chemistry, QD1-999
Abstract

The binary assembly DDA-{Mo132}/OA-γ-Fe2O3 (DDA = didodecyldimethylammonium, {Mo132} = [Mo132O372(CH3COO)30(H2O)72]42−, OA = oleic acid) constitutes one of the two examples in the literature of binary superlattices made of a mixing of nanocrystals and oxo-clusters. In a precedent work, we reported in details the preparation of such magnetic binary systems and studied the effect of the nature of the polyoxometalates (POMs) on the magnetic properties. In the present paper, we study the stability of this model binary assembly under heating at various temperatures. Indeed, especially if magnetic and/or transport properties are targeted, an annealing can be essential to change the phase of the nanocrystals in a more magnetic one and/or to desorb the organic capping of the nano-objects that can constitute an obstacle to the electronic communication between the nano-objects. We gave evidence that the maghemite organization in the binary assembly is maintained until 370°C under vacuum thanks to the presence of the POMs. This latter evolve in the phase MoO3, but still permits to avoid the aggregation of the nanocrystals as well as preserve their periodical arrangement. On the contrary, an assembly made of pure γ-Fe2O3 nanocrystals displays a clear aggregation of the nano-objects from 370°C, as attested by transmission and scanning electronic microscopies and confirmed by magnetic measurements. The stability of the magnetic nanocrystals in such POMs/nanocrystals assemblies opens the way to (i) the elaboration of new binary assemblies from POMs and numerous kinds of nanocrystals with a good control on the magnetic properties and to (ii) the investigation of new physical properties as exchange coupling, or magneto-transport in such systems.

Published
2019
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5. 5-Phenyl-2-(4-pyridyl)pyrimidine

Author

Bernold Hasenknopf, Anna Proust, Garry S. Hanan, Siu Hong Yu, and Marie-Pierre C. Santoni

Subjects
Crystallography, QD901-999
Abstract

The title compound, C15H11N3, crystallizes with two independent molecules in the asymmetric unit. The dihedral angles between the phenyl and pyridine rings in each molecule are 53.48 (5) and 50.80 (5)°. In the crystal structure, weak intermolecular C—H...N hydrogen bonds connect molecules into one-dimensional chains. In addition, the crystal structure is stabilized by weak C—H...π(arene) interactions.

Published
2008
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6. Lennard-Jones interaction parameters of Mo and W in He and N2 from collision cross-sections of Lindqvist and Keggin polyoxometalate anions

Author

Sébastien Hupin, Vincent Tognetti, Frédéric Rosu, Séverine Renaudineau, Anna Proust, Guillaume Izzet, Valérie Gabelica, Carlos Afonso, and Hélène Lavanant

Subjects
General Physics and Astronomy, Physical and Theoretical Chemistry
Abstract

Collision cross-sections of polyoxometalates: molecular modelling completes experimental determination using drift tube ion mobility mass spectrometry.

Published
2022
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9. Redox-controlled conductance of polyoxometalate molecular junctions

Author

Cécile Huez, David Guérin, Stéphane Lenfant, Florence Volatron, Michel Calame, Mickael L. Perrin, Anna Proust, Dominique Vuillaume, Nanostructures, nanoComponents & Molecules - IEMN (NCM - IEMN), Institut d’Électronique, de Microélectronique et de Nanotechnologie - UMR 8520 (IEMN), Centrale Lille-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université Polytechnique Hauts-de-France (UPHF)-JUNIA (JUNIA), Université catholique de Lille (UCL)-Université catholique de Lille (UCL)-Centrale Lille-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université Polytechnique Hauts-de-France (UPHF)-JUNIA (JUNIA), Université catholique de Lille (UCL)-Université catholique de Lille (UCL), 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), Swiss Federal Laboratories for Materials Science and Technology [Dübendorf] (EMPA), University of Basel (Unibas), Eidgenössische Technische Hochschule - Swiss Federal Institute of Technology [Zürich] (ETH Zürich), We acknowledge support of the CNRS, project 'neuroPOM', under a grant of the 80PRIME program. We acknowledge Xavier Wallart (IEMN-CNRS) for his help with the XPS measurements. K. Trinh (IPCM-CNRS) is warmly acknowledged for the synthesis of PMo 12 (0) and PMo 12 (I ), and PCMP PCP

Subjects
Condensed Matter - Materials Science, Condensed Matter - Mesoscale and Nanoscale Physics, molecular electronics, Materials Science (cond-mat.mtrl-sci), FOS: Physical sciences, [CHIM.MATE]Chemical Sciences/Material chemistry, conductive AFM, machine learning, redox, Mesoscale and Nanoscale Physics (cond-mat.mes-hall), polyoxometalate, General Materials Science, electron transport, [PHYS.COND.CM-MSQHE]Physics [physics]/Condensed Matter [cond-mat]/Mesoscopic Systems and Quantum Hall Effect [cond-mat.mes-hall]
Abstract

International audience; We demonstrate the reversible in situ photoreduction of molecular junctions of phosphomolybdate [PMo12O40]3- monolayer self-assembled on flat gold electrodes, connected by the tip of a conductive atomic force microscope. The conductance of the one electron reduced [PMo12O40]4- molecular junction is increased by ∼ 10, this open-shell state is stable in the junction in air at room temperature. The analysis of a large current-voltage dataset by unsupervised machine learning and clustering algorithms reveals that the electron transport in the pristine phosphomolybdate junctions leads to symmetric current-voltage curves, controlled by the lowest unoccupied molecular orbital (LUMO) at 0.6-0.7 eV above the Fermi energy with ∼25% of the junctions having a better electronic coupling to the electrodes than the main part of the dataset. This analysis also shows that a small fraction (∼ 18% of the dataset) of the molecules is already reduced. The UV light in situ photoreduced phosphomolybdate junctions are systematically featuring slightly asymmetric current-voltage behaviors, which is ascribed to electron transport mediated by the single occupied molecular orbital (SOMO) nearly at resonance with the Fermi energy of the electrode and by a closely located single unoccupied molecular orbital (SUMO) at ∼0.3 eV above the SOMO with a weak electronic coupling to the electrodes (∼ 50% of the dataset) or at ∼0.4 eV but with a better electrode coupling (∼ 50% of the dataset). These results shed lights to the electronic properties of reversible switchable redox polyoxometalates, a key point for potential applications in nanoelectronic devices.

Published
2022
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11. Tuning Photoinduced Electron Transfer in POM‐Bodipy Hybrids by Controlling the Environment: Experiment and Theory

Author

Pavel Chábera, Albert Masip-Sánchez, Joshua K. G. Karlsson, Sandra Alves, Tõnu Pullerits, Ian P. Clark, Fiona Black, Georgios Toupalas, Sébastien Blanchard, Xavier López, Josep M. Poblet, Youssef Ben M'Barek, Guillaume Izzet, Anna Proust, Elizabeth A. Gibson, 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), Newcastle University [Newcastle], and Universitat Rovira i Virgili

Subjects
chemistry.chemical_classification, Materials science, 010405 organic chemistry, General Chemistry, General Medicine, 010402 general chemistry, 01 natural sciences, Catalysis, Photoinduced electron transfer, Marcus theory, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, chemistry.chemical_compound, Molecular dynamics, Electron transfer, Solvation shell, chemistry, Chemical physics, Intramolecular force, Counterion, BODIPY, [CHIM.OTHE]Chemical Sciences/Other
Abstract

The optical and electrochemical properties of a series of polyoxometalate (POM) oxoclusters decorated with two bodipy (boron-dipyrromethene) light-harvesting units were examined. Evaluated here in this polyanionic donor-acceptor system is the effect of the solvent and associated counterions on the intramolecular photoinduced electron transfer. The results show that both solvents and counterions have a major impact upon the energy of the charge-transfer state by modifying the solvation shell around the POMs. This modification leads to a significantly shorter charge separation time in the case of smaller counterion and slower charge recombination in a less polar solvent. These results were rationalized in terms of Marcus theory and show that solvent and counterion both affect the driving force for photoinduced electron transfer and the reorganization energy. This was corroborated with theoretical investigations combining DFT and molecular dynamics simulations.

Published
2021
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13. When Identification of the Reduction Sites in Mixed Molybdenum/Tungsten Keggin-Type Polyoxometalate Hybrids Turns Out Tricky

Author

Maxime Laurans, Michele Mattera, Raphaël Salles, Ludivine K’Bidi, Pierre Gouzerh, Séverine Renaudineau, Florence Volatron, Geoffroy Guillemot, Sébastien Blanchard, Guillaume Izzet, Albert Solé-Daura, Josep M. Poblet, and Anna Proust

Subjects
Inorganic Chemistry, Physical and Theoretical Chemistry
Abstract

The mixed molybdenum/tungsten Keggin-type polyoxometalate (POM) hybrid (TBA)

Published
2022

14. Thermodynamics, Electrode Kinetics, and Mechanistic Nuances Associated with the Voltammetric Reduction of Dissolved [n-Bu4N]4[PW11O39{Sn(C6H4)C≡C(C6H4)(N3C4H10)}] and a Surface-Confined Diazonium Derivative

Author

Anisur Rahman, Anna Proust, SiXuan Guo, Maxime Laurans, Jie Zhang, Guillaume Izzet, and Alan M. Bond

Subjects
Energy Engineering and Power Technology, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, 0104 chemical sciences, Reduction (complexity), chemistry.chemical_compound, Amplitude, chemistry, Materials Chemistry, Electrochemistry, Chemical Engineering (miscellaneous), Physical chemistry, Electrical and Electronic Engineering, 0210 nano-technology, Voltammetry, Derivative (chemistry), Electrode kinetics
Abstract

The power of Fourier-transformed large amplitude alternating current voltammetry (FTACV) has been applied to parameterize the reduction of the phosphotungstate [PW11O39{Sn(C6H4)C≡C(C6H4)(N3C4H10)}]...

Published
2020
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15. Immobilization of polyoxometalate hybrid catalysts onto mesoporous silica supports using phenylene diisothiocyanate as a cross-linking agent

Author

Anna Proust, Ourania Makrygenni, Franck Launay, Richard Villanneau, Dalil Brouri, Institut Parisien de Chimie Moléculaire (IPCM), Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Réactivité de Surface (LRS), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Edifices PolyMétalliques (E-POM), 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)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), and Laboratoire de Chimie Inorganique et Matériaux Moléculaires (CIM2)

Subjects
02 engineering and technology, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 01 natural sciences, Catalysis, chemistry.chemical_compound, Aniline, Cyclooctene, Polymer chemistry, [CHIM]Chemical Sciences, Moiety, [CHIM.COOR]Chemical Sciences/Coordination chemistry, General Materials Science, Acetonitrile, ComputingMilieux_MISCELLANEOUS, Chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, [CHIM.MATE]Chemical Sciences/Material chemistry, General Chemistry, Mesoporous silica, 021001 nanoscience & nanotechnology, Condensed Matter Physics, 0104 chemical sciences, Thiourea, Mechanics of Materials, Polyoxometalate, 0210 nano-technology
Abstract

The hybrid derivative of heteropolytungstate bearing two aniline groups, namely (nBu4N)3[NaHPW9O34{As(O)C6H4NH2}2], was post-functionalized in the presence of 1,4-phenylene diisothiocyanate (PDITC). The resulting molecular moiety was characterized by IR, 1H and 31P NMR spectroscopy. In a second step, this post-functionalized hybrid of polyoxometalate was covalently grafted onto the surface of an amino-functionalized SBA-15 silica by means of the formation of thiourea bonds. This simple and efficient strategy of immobilization did not require the use of a coupling agent and was performed in mild reaction conditions. Various physicochemical techniques (13C and 31P CP MAS NMR spectroscopies, XPS, XRF, HR-TEM microscopy and N2 sorption) contributed to the full characterization of the supported catalyst. In addition HR-TEM was found to be an essential technique for the identification of the polyoxometalate units inside the pores of SBA-15. Finally, the catalytic performances of the supported polyoxometalates were evaluated in the epoxidation of cyclooctene with aqueous H2O2 in acetonitrile at 50 °C.

Published
2019
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16. Advantages of Covalent Immobilization of Metal‐Salophen on Amino‐Functionalized Mesoporous Silica in Terms of Recycling and Catalytic Activity for CO 2 Cycloaddition onto Epoxides

Author

Anna Proust, Sébastien Beaudoin, Franck Launay, Matthieu Balas, Richard Villanneau, Laboratoire de Réactivité de Surface (LRS), Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), 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
010405 organic chemistry, Chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, Mesoporous silica, 010402 general chemistry, 01 natural sciences, Combinatorial chemistry, Cycloaddition, 0104 chemical sciences, Amino functionalized, Catalysis, Inorganic Chemistry, Metal, Covalent bond, visual_art, visual_art.visual_art_medium, [CHIM.COOR]Chemical Sciences/Coordination chemistry
Abstract

International audience; NiII and MnIII Schiff base complexes (Salophen-Ni and Salophen-MnCl) bearing a pending carboxylic group were prepared and characterized. Both complexes were grafted onto a mesoporous amino-functionalized SBA-15 silica, by formation of an amide function between the propylamine groups of the support and the carboxylic acid functions of the salophen ligand (corresponding respective to 1.30 wt.% of Ni and 1.06 wt.% of Mn). The co-catalytic behaviour of the free and grafted complexes was then evaluated in the CO2 cycloaddition reaction onto styrene oxide, using tetra-butylammonium bromide (n−Bu4NBr) as the main catalyst. In homogeneous conditions, the MnIII Schiff base complex and the NiII one, to a lesser extent, behave as efficient co-catalysts for this reaction (styrene conversion of 100 % and 65 % respectively after 3 h at 120 °C, under 15 bars of CO2). Upon immobilization at the surface of the amino-functionalized SBA-15, we showed that the co-catalytic activity of the less efficient one, i. e. Ni2+ salophen complex, could be enhanced (reaching a full conversion after 7 h), hence highlighting a potential synergistic effect between the unused amine functions of the support and the Ni2+ salophen co-catalyst. Both salophen complexes were successfully re-used in homogeneous conditions or after their immobilization without any appreciable loss of activity. This work is only a first step towards a completely heterogeneous catalytic system, in which the tetraalkylammonium halide catalyst and the metal-salophen co-catalyst will both be covalently anchored on the same support

Published
2021
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17. Photocurrent Generation from Visible Light Irradiation of Covalent Polyoxometalate-Porphyrin Copolymers

Author

Bonnefont Antoine, Yiming Liang, Hualong Xu, Zhaohui Huo, Edoardo Matricardi, Dejin Zang, Rana Farha, Guillaume Izzet, Anna Proust, Laurent Ruhlmann, Shu Yang, Michel Goldmann, Guangdong University of Education (GDUE), Institut de Chimie de Strasbourg, Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Institut des Nanosciences de Paris (INSP), Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Fudan University [Shanghai], 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
Materials science, organic–inorganic hybrid composites, General Chemical Engineering, porphyrinoids, 02 engineering and technology, 010402 general chemistry, Photochemistry, Electrochemistry, 01 natural sciences, 7. Clean energy, chemistry.chemical_compound, X-ray photoelectron spectroscopy, Copolymer, polyoxometalates, Spectroscopy, Photocurrent, 021001 nanoscience & nanotechnology, Porphyrin, photocurrent generation, 0104 chemical sciences, copolymerization, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, thin films, Covalent bond, Polyoxometalate, 0210 nano-technology
Abstract

International audience; Four hybrid polyoxometalate–porphyrin copolymer films were obtained by the electrooxidation of zinc-β-octaethylporphyrin (ZnOEP) or 5,15-ditolylporphyrin (H2T2P) in the presence of organosilyl functionalized Keggin-type POMs TBA3[PW11Si2O40C26H16N2] (abbreviated Py-PW11Si2-Py) and Dawson-type POMs TBA6[P2W17Si2O62C26H16N2] (abbreviated Py-P2W17Si2-Py) bearing two remote pyridyl groups. The electropolymerization process of the four copolymers was monitored by EQCM. The obtained copolymers were characterized by UV/Vis spectroscopy, X-ray photoelectron spectroscopy, electrochemistry, and AFM. Their impedance properties (EIS) were studied and their photovoltaic performances were also investigated by photocurrent transient measurements under visible light irradiation. These studies showed a correlation between impedance and photovoltaic performances, the films based on Dawson type POMs and Zn porphyrins giving the best results. This last system displayed one of the best photocurrent efficiency for a reported POM photosensitized hybrid.

Published
2021
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18. Polarizability is a key parameter for molecular electronics

Author

Marine Tassé, Phillipe Demont, Sébastien Cher, Sandra Alves, Bruno Chaudret, Angélique Gillet, Florence Volatron, Thomas Blon, Simon Tricard, Anna Proust, Guillaume Izzet, Laboratoire de physique et chimie des nano-objets (LPCNO), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), 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)-Fédération de recherche « Matière et interactions » (FeRMI), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de chimie de coordination (LCC), Institut de Chimie de Toulouse (ICT), Université de Toulouse (UT)-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), Ecole nationale supérieure des ingénieurs en arts chimiques et technologiques (ENSIACET), Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT), Centre interuniversitaire de recherche et d'ingenierie des matériaux (CIRIMAT), Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT), ANR-18-CE09-0007,MOSC,Chimie supraparticulaire orientée par des molécules(2018), 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)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie de Toulouse (ICT-FR 2599), 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-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), 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), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), INP - ENSIACET, Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées, 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 Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC), Centre National de la Recherche Scientifique - CNRS (FRANCE), Institut National Polytechnique de Toulouse - Toulouse INP (FRANCE), Institut National des Sciences Appliquées de Toulouse - INSA (FRANCE), Sorbonne Université (FRANCE), and Université Toulouse III - Paul Sabatier - UT3 (FRANCE)

Subjects
Materials science, Matériaux, Molecular electronics, Heteroatom, Nanoelectronics, Condensed matter, Micro, Coulomb blockade, Charge (physics), 02 engineering and technology, Dielectric, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, 0104 chemical sciences, Polarizability, Chemical physics, Molecule, [CHIM]Chemical Sciences, General Materials Science, 0210 nano-technology
Abstract

International audience; Identifying descriptors that govern charge transport in molecular electronics is of prime importance for the elaboration of devices. The effects of molecule characteristics, such as size, bulkiness or charge, have been widely reported. Herein, we show that the molecule polarizability can be a crucial parameter to consider. To this end, platinum nanoparticle self-assemblies (PtNP SAs) are synthesized in solution, including a series of polyoxometalates (POMs). The charge of the POM unit can be modified according to the nature of the central heteroatom while keeping its size constant. POM hybrids that display remote terminal thiol functions strongly anchor the PtNP surface to form robust SAs. IV curves, recorded by conductive AFM, show a decrease in Coulomb blockade as the dielectric constant of the POMs increases. In this system, charge transport across molecular junctions can be interpreted as variations in polarizability, which is directly related to the dielectric constant.

Published
2021
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19. Society Prizewinner Collection - The Division of Coordination Chemistry of the French Chemical Society

Author

Rinaldo Poli, Anna Proust, 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), Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), and Université Fédérale Toulouse Midi-Pyrénées-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Inorganic Chemistry, chemistry.chemical_classification, chemistry, 010405 organic chemistry, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Division (mathematics), 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Coordination complex, Management, Chemical society
Abstract

International audience; Guest Editors Anna Proust and Rinaldo Poli briefly present the Division of Coordination Chemistry of the French Chemical Society and the annual prize it awards to selected scientists, who are the authors of this Society Prizewinner Collection.

Published
2020
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20. Conductivity via Thermally Induced Gap States in a Polyoxometalate Thin Layer

Author

Cindy L. Rountree, Amanda Generosi, Barbara Paci, Anna Proust, Qirong Zhu, Claire Mathieu, Nicholas Barrett, Guillaume Izzet, Pierre Gouzerh, Séverine Renaudineau, Ludovic Tortech, Xihui Liang, 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), Laboratoire Innovation en Chimie des Surfaces et NanoSciences (LICSEN), Nanosciences et Innovation pour les Matériaux, la Biomédecine et l'Energie (ex SIS2M) (NIMBE UMR 3685), Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Consiglio Nazionale delle Ricerche [Roma] (CNR), Service de physique de l'état condensé (SPEC - UMR3680), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), DIM NanoK, région Ile de France, 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), 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), Laboratoire Innovation en Chimie des Surfaces et NanoSciences (LICSEN UMR 3685), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and National Research Council of Italy | Consiglio Nazionale delle Ricerche (CNR)

Subjects
Materials science, Photoemission spectroscopy, 02 engineering and technology, Conductivity, 010402 general chemistry, 7. Clean energy, 01 natural sciences, Polyoxometalate Thin Layer, Physical and Theoretical Chemistry, Electrical conductor, Deposition (law), business.industry, Thermally Induced Gap- States, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, Thermal conduction, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Characterization (materials science), General Energy, Polyoxometalate, Optoelectronics, 0210 nano-technology, business, Layer (electronics)
Abstract

International audience; We report a study of alpha-[P2W18O62]6-, Wells-Dawson polyoxometalate layers deposited on ITO coated glass substrates. A variety of techniques has been used including atomic force microscopy for surface topography characterization, current mapping and current-voltage characteristics, X-ray photoemission spectroscopy for chemical analysis, UV-visible photoemission spectroscopy for determination of band line-ups and energy dispersive X-ray reflectivity for determination of layer thicknesses and scattering length densities. The conditions of film deposition and subsequent thermal annealing strongly affect the film characteristics. In particular, we show that nanostriped films a few tens of nm thick can be obtained in a reproducible manner and that such structuring is accompanied by the appearance of gap-states and by a switch from an insulating to a conductive state. Current-voltage characteristics demonstrate that highly ordered films of K 6 [P 2 W 18 O 62 ] allow electron flow only from ITO to [P2W18O62]6-, thus showing a rectifying effect. Finally, we integrate the POM layer 2 into an organic photovoltaic device and show the conduction through it thanks to favorable band alignment between ITO, the gap states and the active photovoltaic layers.

Published
2019
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21. Assessing the Electrocatalytic Properties of the {Cp*Rh III } 2+ ‐Polyoxometalate Derivative [H 2 PW 11 O 39 {Rh III Cp*(OH 2 )}] 3– towards CO 2 Reduction

Author

Anna Proust, Marcelo Girardi, Dominique Platzer, Sébastien Blanchard, Fethi Bedioui, Sophie Griveau, and Sandra Alves

Subjects
010405 organic chemistry, Ligand, 010402 general chemistry, 7. Clean energy, 01 natural sciences, Medicinal chemistry, Redox, Non-innocent ligand, 0104 chemical sciences, Catalysis, Inorganic Chemistry, Bipyridine, chemistry.chemical_compound, chemistry, Polyoxometalate, Formate, Acetonitrile
Abstract

Storage of electricity produced intermittently by renewable energy sources is a societal issue. Besides the use of batteries and supercapacitors, conversion of excess electricity into chemical energy is also actively investigated. The conversion of CO2 to fuel or fuel precursors is an option that requires the use of a catalyst to overcome the high activation energy barrier. Of molecular catalysts, metal complexes with polypyridyl ligands are well represented, among which the [Cp*Rh(bpy)Cl] + and [M(bpy)(CO)3X] (M = Re, Mn) complexes. As redox non-innocent ligand, the bipyridine ligand is generally involved in the reduction mechanisms. It is thus tempting to replace it by other redox non-innocent ligands such as vacant polyoxometalates (POMs). We have thus prepared [α-H2PW11O39{Rh(III)Cp*(OH2}] 3-which is closely related to [Cp*Rh(III)(bpy)Cl] + by substitution of the monovacant [PW11O39] 7-Keggin-type POM for the bipyridine ligand. Its activity towards CO2 reduction has been assessed in acetonitrile in the presence of water. Compared to [Cp*Rh(bpy)Cl] + that produces formate selectively over CO and H2, the POM derived catalyst favours proton reduction over CO2 reduction.

Published
2018
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22. Self-assembly study of nanometric spheres from polyoxometalate-phenylalanine hybrids, an experimental and theoretical approach

Author

Chrysoula Kokotidou, Anna Proust, Athanassios G. Coutsolelos, Jorge J. Carbó, Asterios Charisiadis, Georgios Charalambidis, Guillaume Izzet, Kostas Karikis, Josep M. Poblet, Maxime Laurans, Emmanouil Nikoloudakis, Antonios M. Douvas, Albert Solé-Daura, Anna Mitraki, Laboratory of Bioinorganic Chemistry, Department of Chemistry [Heraklion], University of Crete [Heraklion] (UOC)-University of Crete [Heraklion] (UOC), 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), University of Crete [Heraklion] (UOC), Departament de Química Física i Inorgànica, Universitat Rovira i Virgili, Edifices PolyMétalliques (E-POM), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Chimie Moléculaire de Paris Centre (FR 2769), Department of Materials Science and Technology, Institute of Nanoscience and Nanotechnology 'Demokritos' [Greece] (INN), and National Center for Scientific Research 'Demokritos' (NCSR)

Subjects
animal structures, Surface Properties, Phenylalanine, Supramolecular chemistry, 02 engineering and technology, Molecular Dynamics Simulation, 010402 general chemistry, 01 natural sciences, Micelle, Inorganic Chemistry, Hydrophobic effect, chemistry.chemical_compound, Organometallic Compounds, [CHIM]Chemical Sciences, Molecule, Particle Size, Diphenylalanine, Molecular Structure, Tungsten Compounds, 021001 nanoscience & nanotechnology, E-POM, 0104 chemical sciences, Solvent, Crystallography, chemistry, Polyoxometalate, Microscopy, Electron, Scanning, Quantum Theory, sense organs, Self-assembly, 0210 nano-technology
Abstract

Herein, we report on the study of supramolecular assemblies based on polyoxometalates (POMs) upon their modification with amino acids. Two POM-amino acid hybrids were synthesized by coupling a functionalized Keggin type polyoxoanion [PW11O39{Sn(C6H4)C[triple bond, length as m-dash]C(C6H4)COOH}]4- with carboxyl-protected (methyl-ester) phenylalanine or diphenylalanine peptides. Surprisingly, all compounds, including the initial POM, formed supramolecular nanospheres in different solvent mixtures, which were examined by scanning electron microscopy (SEM). Molecular dynamics (MD) simulations for the POM-amino acid species revealed that the hydrophobic forces are mainly responsible for the initial aggregation into incipient micelle type structures, in which the organic arms are buried inside the aggregate while POM polar heads are more exposed to the solvent with tetrabutyl-ammonium counter cations acting as linkers.

Published
2018
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23. Polyoxometalates in the Hofmeister series

Author

Thomas Buchecker, Arno Pfitzner, Séverine Renaudineau, Anna Proust, Philipp Schmid, Olivier Diat, Pierre Bauduin, Universität Regensburg (UR), 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), Ions aux Interfaces Actives (L2IA), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), 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), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), and Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)

Subjects
Hofmeister series, Computer science, ddc:540, Cloud computing, nano-ions, 010402 general chemistry, superchaotrope, 01 natural sciences, Catalysis, polyoxometallate, Simple (abstract algebra), Materials Chemistry, Point (geometry), Statistical physics, cloud point, Cloud point, 010405 organic chemistry, business.industry, Metals and Alloys, General Chemistry, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, 540 Chemie, Ceramics and Composites, Polar, business, [PHYS.COND.CM-SCM]Physics [physics]/Condensed Matter [cond-mat]/Soft Condensed Matter [cond-mat.soft]
Abstract

International audience; We propose a simple experimental procedure based on the cloud point measurement of a non-ionic surfactant as a tool for (i) esti-mating the super-chaotropic behaviour of polyoxometalate (POMs) and for (ii) establishing a classification of POMs according to their affinity towards polar surfaces.

Published
2018
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25. Selective Formation of Epoxylimonene Catalyzed by Phosphonyl/Arsonyl Derivatives of Trivacant Polyoxotungstates at Low Temperature

Author

Ourania Makrygenni, Alain Shum Cheong Sing, Hélène Gérard, Sabrina Taourit, Richard Villanneau, Anna Proust, Franck Launay, Louise Vanmairis, 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), Laboratoire de Chimie des Substances Naturelles et des Sciences des Aliments (LCSNSA), Université de La Réunion (UR), Laboratoire de Réactivité de Surface (LRS), Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Physique et Chimie Théoriques (LPCT), Institut de Chimie du CNRS (INC)-Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de chimie théorique (LCT), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Laboratoire de Chimie Inorganique et Matériaux Moléculaires (CIM2)

Subjects
Limonene, 010405 organic chemistry, Homogeneous catalysis, [CHIM.CATA]Chemical Sciences/Catalysis, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Catalysis, Inorganic Chemistry, chemistry.chemical_compound, chemistry, Organic chemistry, [CHIM]Chemical Sciences
Abstract

International audience; The catalytic performances of three organophosphonyle/arsonyle derivatives of POMs were evaluated for the epoxidation of limonene in acetonitrile, using aqueous H2O2 as the oxidant. All three W-based POMs catalysts operated without any additional transition-metal ions and displayed excellent conversion for the limonene to temperatures varying from 4 to 50°C. Furthermore, the use of B,α−[NaHAsW9O33{P(O)R}2] 3-(R = t Bu,-CH2CH2CO2H) complexes led to the complete conversion of limonene to epoxylimonene at 4°C. The selectivity of the reaction was modulated by varying the reaction solvent, and it was found that allylic reactions were favoured in ethanol. The effect of the catalyst protonation was also investigated by DFT calculations, highlighting the role of protons in the epoxidation process.

Published
2020
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26. Hierarchical Self-Assembly of Polyoxometalate-Based Organo Palladium(II) Metallomacrocycles via Electrostatic Interactions

Author

Raphaël Salles, Anna Proust, Aurélie Bernard, Guillaume Izzet, Christophe Desmarets, Qichun Zhang, Dalil Brouri, Etienne Derat, Benjamin Abécassis, 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), Laboratoire de Physique des Solides (LPS), Centre National de la Recherche Scientifique (CNRS)-Université Paris-Sud - Paris 11 (UP11), 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), Méthodes et Application en Chimie Organique (MACO), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Chimie Moléculaire de Paris Centre (FR 2769), Laboratoire de Réactivité de Surface (LRS), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Sorbonne Université (SU), Nanyang Technological University [Singapour], Edifices PolyMétalliques (E-POM), Architectures Moléculaires (A.R.C), 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), 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), Université Paris-Sud - Paris 11 (UP11)-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), 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)-Chimie Moléculaire de Paris Centre (FR 2769)

Subjects
010405 organic chemistry, Small-angle X-ray scattering, POLE 2, POLE 1, Supramolecular chemistry, Solvation, chemistry.chemical_element, Ethylenediamine, 010402 general chemistry, 01 natural sciences, E-POM, ARC, 0104 chemical sciences, Inorganic Chemistry, chemistry.chemical_compound, Crystallography, chemistry, Polyoxometalate, [CHIM]Chemical Sciences, Self-assembly, Physical and Theoretical Chemistry, MACO, Protic solvent, Palladium
Abstract

International audience; The design and synthesis of a supramolecular square composed of polyoxometalate-based hybrid donors and ethylenediamine palladium(II) nodes are reported. The structure of the metallomacrocycle scaffold was inferred by diffusion NMR, small-angle X-ray scattering (SAXS), and molecular modeling. The metallomacrocycle scaffold that contains negatively and positively charged subunits can further self-assemble owing to a competition between the solvation energy of the discrete species and intermolecular electrostatic interactions. When the dissociating character of the solvent was lowered or when in the presence of a protic solvent, different types of multiscale organizations (vesicles and pseudo-1D structures) were selectively formed and were characterized by SAXS and transmission electron microscopy.

Published
2020
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27. Dye-Sensitized Photocathodes: Boosting Photoelectrochemical Performances with Polyoxometalate Electron Transfer Mediators

Author

Vincent Artero, Florence Volatron, Youssef Ben M'Barek, Raphaël Salles, Sébastien Blanchard, Murielle Chavarot-Kerlidou, Matthieu Koepf, Jérémy Sum, Jennifer Fize, Timothy E. Rosser, Anna Proust, Guillaume Izzet, 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), Solar fuels, hydrogen and catalysis (SolHyCat), Laboratoire de Chimie et Biologie des Métaux (LCBM - UMR 5249), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-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)-Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-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)-Université Grenoble Alpes (UGA), 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), 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), ANR-16-CE05-0025,PhotoCarb,Photosynthèse artificielle: du CO2 aux carburants(2016), and ANR-17-EURE-0003,CBH-EUR-GS,CBH-EUR-GS(2017)

Subjects
Materials science, Boosting (machine learning), redox mediator, Energy Engineering and Power Technology, 02 engineering and technology, 010402 general chemistry, Photochemistry, 01 natural sciences, photoelectrochemical cells, law.invention, Electron transfer, law, Materials Chemistry, Electrochemistry, photocathodes, Chemical Engineering (miscellaneous), [CHIM]Chemical Sciences, polyoxometalates, Electrical and Electronic Engineering, nano-ITO, [CHIM.MATE]Chemical Sciences/Material chemistry, Photoelectrochemical cell, 021001 nanoscience & nanotechnology, Cathode, 0104 chemical sciences, Polyoxometalate, 0210 nano-technology, Redox mediator
Abstract

International audience; The amplification effect of polyoxometalates (POMs) on the efficiency of dye-sensitized nano-ITO cathodes is disclosed. The use of hybrid polyoxometalates of the type [PW11O39{SnC6H4 C6H4F}](4-), F standing for a carboxylic group (POM-COOH) or a diazonium unit, allows control of the loading of the POMs on the electrode and investigation of key parameters. Even at very low loading, POM-COON has a substantial effect on the photocurrent response with up to 25-fold increase. Besides ensuring the stability toward leaching, the anchoring function of the POM hybrids was also found to play an intricate role in the competition between the multiple events involved.

Published
2020
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28. Catalyst Design for Alkene Epoxidation by Molecular Analogues of Heterogeneous Titanium-Silicalite Catalysts

Author

Hugo Fouilloux, Albert Solé-Daura, Jorge J. Carbó, Lise-Marie Chamoreau, Anna Proust, Teng Zhang, Christophe M. Thomas, Geoffroy Guillemot, Carine Robert, Josep M. Poblet, Universitat Rovira i Virgili, 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), Institut de Recherche de Chimie Paris (IRCP), 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), Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL), and Departament de Química Física i Inorgànica

Subjects
Allylic rearrangement, Molecular model, 010405 organic chemistry, chemistry.chemical_element, General Chemistry, Alkene epoxidation, 010402 general chemistry, 01 natural sciences, Catalysis, 0104 chemical sciences, Silanol, chemistry.chemical_compound, chemistry, Polymer chemistry, [CHIM]Chemical Sciences, Titanium
Abstract

International audience; The epoxidation of allylic alcohols with H2O2 catalyzed by the hybrid [α-B-SbW9O33(tBuSiO)3Ti(OiPr)]3\textendash (1) anion as a molecular model of heterogeneous Ti-silicalite TS-1 catalyst was analyzed by means of DFT to determine the main factors that control the catalytic process and, finally, to improve the value of the available catalysts. Our calculations revealed that unlike other alkenes, allylic alcohols can bind the Ti center after activation of the precatalyst via hydrolysis to give the corresponding Ti-alcoholate, which is the catalyst resting state. Next, the dissociative addition of hydrogen peroxide to Ti causes the cleavage of a Ti\textendash OSi junction to form a Ti(\eta2-OOH) moiety. The partial detachment of the Ti from the catalyst structure yields an intermediate with a flexible Ti center from which the Ti-OOH group can transfer an electrophilic oxygen to the alkene substrate in an inner-sphere fashion. The rate-determining process, which involves the heterolytic activation of H2O2 over the Ti(IV) and the electrophilic O-transfer, accounts for an overall free-energy barrier of 23.0 kcal mol\textendash 1 for 2-methyl-2-buten-1-ol, in line with the experimental value of 22.3. Conversely, the outer-sphere O-transfer\textemdash also accessible to nonfunctionalized alkenes\textemdash occurs through a more strained transition state that lays above in energy (by ∼4 kcal mol\textendash 1), giving a clue to explain the low yields reported experimentally for nonfunctionalized olefins. We also found that reducing the bulkiness of the substituents in the silanol functions of the catalyst has a positive influence on the catalytic activity, decreasing the overall free-energy barriers for the outer-sphere path. With this knowledge, we developed other catalytic species with tailored steric properties based on [SbW9O33(RSiOH)3]3\textendash structure (R =iPr and nPr), which were synthesized, characterized, and successfully applied to the catalytic epoxidation of unfunctionalized alkenes. Present results clearly show that the detailed knowledge of the reaction mechanisms, even for complex processes, is possible nowadays and that the acquired information allows designing catalysts with desired activities.

Published
2020
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29. Protective Effect of Polyoxometalates in {Mo 132 }/Maghemite Binary Superlattices Under Annealing

Author

Romain Breitwieser, Adrien Garnier, Thomas Auvray, Anh-Tu Ngo, Benoit Baptiste, Nicolas Menguy, Anna Proust, Christophe Petit, Florence Volatron, Caroline Salzemann, De la Molécule aux Nanos-objets : Réactivité, Interactions et Spectroscopies (MONARIS), Institut de Chimie du CNRS (INC)-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), 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), 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
Materials science, Annealing (metallurgy), Magnetism, Superlattice, Maghemite, Binary number, 02 engineering and technology, engineering.material, 010402 general chemistry, 01 natural sciences, lcsh:Chemistry, binary superlattices, Desorption, [CHIM]Chemical Sciences, polyoxometalates, General Chemistry, 021001 nanoscience & nanotechnology, 0104 chemical sciences, maghemite, Nanocrystal, lcsh:QD1-999, Chemical physics, magnetism, Polyoxometalate, engineering, annealing, 0210 nano-technology
Abstract

International audience; The binary assembly DDA-{Mo 132 }/OA-γ-Fe 2 O 3 (DDA = didodecyldimethylammonium, {Mo 132 } = [Mo 132 O 372 (CH 3 COO) 30 (H 2 O) 72 ] 42− , OA = oleic acid) constitutes one of the two examples in the literature of binary superlattices made of a mixing of nanocrystals and oxo-clusters. In a precedent work, we reported in details the preparation of such magnetic binary systems and studied the effect of the nature of the polyoxometalates (POMs) on the magnetic properties. In the present paper, we study the stability of this model binary assembly under heating at various temperatures. Indeed, especially if magnetic and/or transport properties are targeted, an annealing can be essential to change the phase of the nanocrystals in a more magnetic one and/or to desorb the organic capping of the nano-objects that can constitute an obstacle to the electronic communication between the nano-objects. We gave evidence that the maghemite organization in the binary assembly is maintained until 370 • C under vacuum thanks to the presence of the POMs. This latter evolve in the phase MoO 3 , but still permits to avoid the aggregation of the nanocrystals as well as preserve their periodical arrangement. On the contrary, an assembly made of pure γ-Fe 2 O 3 nanocrystals displays a clear aggregation of the nano-objects from 370 • C, as attested by transmission and scanning electronic microscopies and confirmed by magnetic measurements. The stability of the magnetic nanocrystals in such POMs/nanocrystals assemblies opens the way to (i) the elaboration of new binary assemblies from POMs and numerous kinds of nanocrystals with a good control on the magnetic properties and to (ii) the investigation of new physical properties as exchange coupling, or magneto-transport in such systems.

Published
2019
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30. Selective uptake of La3+ ions with polyoxometalates-functionalized mesoporous SBA-15: An EXAFS study

Author

Franck Launay, Richard Villanneau, Dalil Brouri, Faiza Bentaleb, Ourania Makrygenni, Anna Proust, 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), Laboratoire de Réactivité de Surface (LRS), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Edifices PolyMétalliques (E-POM), 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), and Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Exafs spectroscopy, chemistry.chemical_element, 02 engineering and technology, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 01 natural sciences, Ion, Lanthanum, Polymer chemistry, [CHIM]Chemical Sciences, General Materials Science, Chelation, ComputingMilieux_MISCELLANEOUS, Extended X-ray absorption fine structure, Polyoxometalates, General Chemistry, Nuclear magnetic resonance spectroscopy, [CHIM.CATA]Chemical Sciences/Catalysis, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, 0104 chemical sciences, EXAFS, chemistry, Mechanics of Materials, Polyoxometalate, 0210 nano-technology, Mesoporous material, Mesoporous silica
Abstract

In this work, mesoporous materials based on inorganic/organic polyoxometalate (POMs) hybrids with the ability of further incorporating heterometallic lanthanum cations were designed. On the basis of the La3+ coordination to vacant organophosphonyle derivatives of POMs previously studied, herein POMs-grafted onto an amino-functionalized mesoporous SBA-15 ({NH2}-SBA-15) with incorporated La3+ ions were synthesized by varying the amounts of the latter. LIII-edge La EXAFS spectroscopy of the resulting materials provided local structural information around LaIII ions (i.e. number, nature and distances of neighboring atoms), which are comparable to that of the LaIII complexes of POMs hybrids. This technique, in addition with 31P CP-MAS NMR spectroscopy, gave definitive clues for a selective uptake of the incorporated La3+ ions by the POMs grafted onto the {NH2}-SBA-15 supports. This study is a clear demonstration that, due to their chelate effect, POMs hybrids act as efficient ligands for La3+ even in the presence of competitive adsorption sites. Consequently, a regular distribution of the La3+ ions along the channels of the SBA-15 is thus observed in these materials due to the nanostructuration of the POMs onto the support.

Published
2019
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31. Evidence for Charge Transfer at the Interface between Hybrid Phosphomolybdate and Epitaxial Graphene

Author

Anass Benayad, Loïc Huder, Mira Baraket, Lionel Dubois, Guillaume Izzet, Louis Jansen, Anna Proust, Florence Duclairoir, Felipe Lipp-Bregolin, Corentin Rinfray, D. Rouchon, Gérard Lapertot, Laboratoire de Transport Electronique Quantique et Supraconductivité (LaTEQS), PHotonique, ELectronique et Ingénierie QuantiqueS (PHELIQS), Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-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)-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 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), 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)), Laboratoire d'Innovation pour les Technologies des Energies Nouvelles et les nanomatériaux (LITEN), Institut National de L'Energie Solaire (INES), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-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), 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), Edifices PolyMétalliques (E-POM), 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), Instrumentation, Material and Correlated Electrons Physics (IMAPEC), ANR-10-NANO-0004,Grafonics,Graphène fonctionnalisé : Application en électronique C-MOS hybride(2010), 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), and 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)

Subjects
Materials science, Inorganic chemistry, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, law.invention, symbols.namesake, X-ray photoelectron spectroscopy, law, Electrochemistry, [CHIM]Chemical Sciences, General Materials Science, Electronic band structure, ComputingMilieux_MISCELLANEOUS, Spectroscopy, Graphene oxide paper, Graphene, Surfaces and Interfaces, 021001 nanoscience & nanotechnology, Condensed Matter Physics, 0104 chemical sciences, Chemical engineering, Polyoxometalate, symbols, Cyclic voltammetry, 0210 nano-technology, Raman spectroscopy, Graphene nanoribbons
Abstract

The interfacing of polyoxometalates and graphene can be considered to be an innovative way to generate hybrid structures that take advantage of the properties of both components. Polyoxometalates are redox-sensitive and photosensitive compounds with high temperature stability (up to 400 °C for some), showing tunable properties depending on the metal incorporated inside the complex. Graphene has a unique electronic band structure combined with good material properties for electrical and optical applications. The spontaneous, rather than electrochemical, functionalization of epitaxial graphene on SiC with Keggin phosphomolybdate derivative TBA3[PMo11O39{Sn(C6H4)C≡C(C6H4)N2}] (named K(Mo)Sn[N2(+)]) bearing a phenyl diazonium unit is investigated. Graphene decoration is evidenced by means of AFM, Raman, XPS, and cyclic voltammetry, indicating a successful immobilization of the polyoxomolybdate. The covalent bonding of the polyoxometalate to the graphene substrate can be deduced from the appearance of a D band in the Raman spectra and from the loss of mobility in the electrical conduction. High-resolution XPS spectra reveal an electron transfer from the graphene to the Mo complex. The comparison of charge-carrier density measurements before and after grafting supports the p-type doping effect, which is further evidenced by work function UPS measurements.

Published
2016
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32. Polyoxometalate as Control Agent for the Doping in HgSe Self-Doped Nanocrystals

Author

Elisa Meriggio, Mathieu G. Silly, Emmanuel Lhuillier, Hervé Cruguel, Emmanuelle Lacaze, Clément Livache, Bertille Martinez, Florence Volatron, Gregory Cabailh, Sandrine Ithurria, Xiang Zhen Xu, Anna Proust, Physico-chimie et dynamique des surfaces (INSP-E6), Institut des Nanosciences de Paris (INSP), Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), Oxydes en basses dimensions (INSP-E9), Laboratoire de Physique et d'Etude des Matériaux (UMR 8213) (LPEM), 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)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie Inorganique et Matériaux Moléculaires (CIM2), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Synchrotron SOLEIL (SSOLEIL), Centre National de la Recherche Scientifique (CNRS), Sorbonne Université (SU), Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), ANR-11-IDEX-0004,SUPER,Sorbonne Universités à Paris pour l'Enseignement et la Recherche(2011), and European Project: 756225,blackQD

Subjects
Materials science, Physics::Optics, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, nanocrystal, Condensed Matter::Superconductivity, self doping, Physical and Theoretical Chemistry, Absorption (electromagnetic radiation), Astrophysics::Galaxy Astrophysics, Plasmon, POM, business.industry, Doping, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, General Energy, Polyoxometalate, Optoelectronics, Condensed Matter::Strongly Correlated Electrons, 0210 nano-technology, business, Doped nanocrystals
Abstract

International audience; Intraband and plasmonic transitions have appeared over the last years as an interesting tool to achieve optical absorption in the mid infrared. Tuning the doping magnitude has become a major challenge not only to tune the optical spectrum but also properties such as the dark current or the time response. Here we investigate the case of self-doped HgSe colloidal quantum dots (CQDs). Tuning of the doping was so far relying on band bending induced by a dipole design at the nanoparticle surface. With such a surface gating approach, it is difficult to conciliate both the massive tuning of the Fermi level with the preservation of transport properties of the CQD arrays. Here we propose a strategy to graft functionalized polyoxometalates (POMs) at the CQD surface and obtain simultaneously a massive tuning of the carrier density (≈5 electrons per nanoparticle) and conduction properties. We bring a consistent demonstration of the HgSe CQD doping decrease by a charge transfer to the POM. This method is highly promising for large tuning of carrier density in degenerately doped semiconductor nanoparticles.

Published
2018
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33. Control of the hierarchical self-assembly of polyoxometalate-based metallomacrocycles by redox trigger and solvent composition

Author

Madeleine, Piot, Benjamin, Abécassis, Dalil, Brouri, Claire, Troufflard, Anna, Proust, and Guillaume, Izzet

Subjects
Chemistry, Physical Sciences, molecular carrier, polyoxometalates, SAXS, hierarchical self-assembly, organic–inorganic hybrids
Abstract

Significance Hierarchical self-assembly is a powerful route allowing the elaboration of complex supramolecular architectures with emergent structuration or properties. Starting from well-defined molecular building units, this synthetic strategy relies on the construction of a preassembled structural motif that can further self-assemble through additional noncovalent interactions. In this context, we developed a system based on a covalent organic–inorganic polyoxometalate hybrid building block combining metal-driven self-assembly and electrostatic interactions. We herein show that in this system, the supramolecular organization can be controlled by a redox stimulus and/or the solvent composition giving rise to various types of nanoarchitectures from discrete metallomacrocycles to 1D worm-like nanoobjects., Discrete metallomacrocycles are attractive scaffolds for the formation of complex supramolecular architectures with emergent properties. We herein describe the formation of hierarchical nanostructures using preformed metallomacrocycles by coordination-driven self-assembly of a covalent organic–inorganic polyoxometalate (POM)-based hybrid. In this system, we take advantage of the presence of charged subunits (POM, metal linker, and counterions) within the metallomacrocycles, which drive their aggregation through intermolecular electrostatic interactions. We show that the solvent composition and the charge of the metal linker are key parameters that steer the supramolecular organization. Different types of hierarchical self-assemblies, zero-dimensional (0D) dense nanoparticles, and 1D worm-like nanoobjects, can be selectively formed owing to different aggregation modes of the metallomacrocycles. Finally, we report that the worm-like structures drastically enhance the solubility in water of a pyrene derivative and can act as molecular carriers.

Published
2018

34. Surface Organization of Polyoxometalate Hybrids Steered by a 2D Supramolecular PTCDI/Melamine Network

Author

Nicolas Battaglini, Florence Volatron, Sandra Alves, Philippe Lang, Andrés Lombana, Philippe Decorse, Guillaume Izzet, Corentin Rinfray, Anna Proust, Interfaces, Traitements, Organisation et Dynamique des Systèmes (ITODYS (UMR_7086)), Université Paris Diderot - Paris 7 (UPD7)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut Parisien de Chimie Moléculaire (IPCM), 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), Centre National de la Recherche Scientifique (CNRS)-Université Paris Diderot - Paris 7 (UPD7), Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), Université Pierre et Marie Curie (Paris 6), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université Paris Diderot - Paris 7 (UPD7)-Centre National de la Recherche Scientifique (CNRS), INSERM U955, équipe 21, Service de néphrologie et transplantation, Assistance publique - Hôpitaux de Paris (AP-HP) (APHP)-Hôpital Henri Mondor-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Assistance publique - Hôpitaux de Paris (AP-HP) (APHP)-Hôpital Henri Mondor-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Institut Mondor de Recherche Biomédicale (IMRB), and Institut National de la Santé et de la Recherche Médicale (INSERM)-IFR10-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Institut National de la Santé et de la Recherche Médicale (INSERM)-IFR10-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)

Subjects
Hydrogen bond, Supramolecular chemistry, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, chemistry.chemical_compound, General Energy, chemistry, X-ray photoelectron spectroscopy, Covalent bond, Diimide, Polymer chemistry, Polyoxometalate, [CHIM]Chemical Sciences, Organic chemistry, Physical and Theoretical Chemistry, 0210 nano-technology, Melamine, Science, technology and society, ComputingMilieux_MISCELLANEOUS
Abstract

A 2D supramolecular honeycomb network built on hydrogen bonding of perylene-3,4,9,10-tetracarboxylic acid diimide (PTCDI) and 1,3,5-triazine-2,4,6-triamine (Melamine) has been self-assembled on Au(111) by a solution processed method. The ability of the porous network to host functional molecular oxides or polyoxometalates (POMs) has been investigated using a functionalized species [PW11O39Ge{p-C6H4-C≡C–C6H4-NHC(O) (CH2)4{-CH(CH2)2S-S-}}]4– (KWGe[S-S]): this inorganic/organic hybrid built on a Keggin-type POM core and an organic tether incorporating a thioctic acid function has been designed to enhance the host–guest interaction by the formation of covalent Au–S bonds. XPS analysis confirmed the presence of the POMs that are covalently held onto the surface. Probed by STM operating under ambient conditions, the spatial organization of the POMs display some reminiscence of the organic template, while monitoring the POM deposition at various immersion times by PM-IRRAS showed that the POM raising at the subs...

Published
2016
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35. Electro‐Assisted Reduction of CO 2 to CO and Formaldehyde by (TOA) 6 [α‐SiW 11 O 39 Co(_)] Polyoxometalate

Author

Marcelo Girardi, Philippe Simon, Fethi Bedioui, Sophie Griveau, Marc Fontecave, Anna Proust, Sébastien Blanchard, 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), Unité de Technologies Chimiques et Biologiques pour la Santé (UTCBS - UM 4 (UMR 8258 / U1022)), 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 Paris Cité (UPCité), Laboratoire de Chimie des Processus Biologiques (LCPB), Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), and GRIVEAU, SOPHIE

Subjects
Electrolysis, Coordination sphere, 010405 organic chemistry, Chemistry, Inorganic chemistry, 010402 general chemistry, Electrocatalyst, Electrochemistry, 01 natural sciences, 0104 chemical sciences, Catalysis, law.invention, Inorganic Chemistry, law, [CHIM] Chemical Sciences, Polyoxometalate, [CHIM]Chemical Sciences, Cyclic voltammetry, Selectivity
Abstract

International audience; We report here on the multiproton-multielectron electrochemical reduction of CO2 in homogeneous solution by using (TOA)6[α-SiW11O39Co(_)] (TOA = tetraoctyl ammonium; _ = vacant position in the coordination sphere of Co) as an electrocatalyst. First, the electrochemical behavior of (TOA)6[α-SiW11O39Co(_)] was analyzed in detail by cyclic voltammetry in dichloromethane, studying the influence of the presence of protons and/or CO2. These preliminary results were further used to optimize the conditions of electrolysis in terms of reduction potentials. Analysis of the electrolysis products in the gas and liquid phases show the formation of CO and HCHO without formation of H2. Our results tend to show that the (TOA)6[α-SiW11O39Co(_)] polyoxometalate is a catalyst for CO2 electroreduction, with unique selectivity.

Published
2015
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36. Rapid photoinduced charge injection into covalent polyoxometalate-bodipy conjugates

Author

Fiona A. Black, Sandra Alves, Aurélie Jacquart, Guillaume Izzet, Georgios Toupalas, Anna Proust, Ian P. Clark, and Elizabeth A. Gibson

Subjects
Materials science, 010405 organic chemistry, General Chemistry, Chromophore, 010402 general chemistry, Photochemistry, 01 natural sciences, 7. Clean energy, Photoinduced electron transfer, 0104 chemical sciences, chemistry.chemical_compound, Chemistry, chemistry, Covalent bond, Polyoxometalate, Ultrafast laser spectroscopy, Surface modification, BODIPY, Spectroscopy
Abstract

A series of redox tunable polyoxometalate–bodipy conjugates display variable charge transfer dynamics occuring down to 54 ps., Controlled design of photoactive hybrids would provide highly active materials for solar energy conversion and photo(electro) catalysis. We describe the kinetics of photoinduced electron transfer in a series of photoactive hybrids based on Keggin-type polyoxometalates (POMs) covalently grafted to bodipy photosensitizers. We show how the electronic properties and corresponding dynamics of these hybrids can be readily tuned by varying the POM metal ion, the anchoring functionalization and the spacer length. Ultrafast visible and IR transient absorption spectroscopy, supported by spectroelectrochemical measurements, reveals that photoinduced electron transfer from the bodipy chromophore to the organosilyl POM derivative occurs as rapidly as τ = 54 ps to generate a long-lived (τ = 4.8 ns) charge-separated (CS) state, making this system appropriate for applications in photoelectrochemical devices.

Published
2018

37. A calibration framework for the determination of accurate collision cross sections of polyanions using polyoxometalate standards

Author

Carlos Afonso, Hélène Lavanant, Michael Groessl, Sébastien Hupin, Séverine Renaudineau, Anna Proust, Guillaume Izzet, Chimie Organique et Bioorganique : Réactivité et Analyse (COBRA), Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie Organique Fine (IRCOF), Université de Rouen Normandie (UNIROUEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Institut Parisien de Chimie Moléculaire (IPCM), Université Pierre et Marie Curie - Paris 6 (UPMC)-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), 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
Drift tube, Chemistry, Ion-mobility spectrometry, 010401 analytical chemistry, Organic Chemistry, Analytical chemistry, 010402 general chemistry, Collision, 01 natural sciences, 0104 chemical sciences, Analytical Chemistry, Ion, Polyoxometalate, Calibration, Traveling wave, [CHIM]Chemical Sciences, Spectroscopy
Abstract

RATIONALE Polyoxometalates (POMs) are remarkable oxo-clusters forming compact highly charged anions. We measured their collision cross sections (CCS) in N2 with drift tube ion mobility spectrometry (DTIMS). These values were then used to calibrate a traveling wave ion mobility spectrometry (TWIMS) device and the accuracy of the calibration was tested. METHODS Six POM standards were analyzed by DTIM-MS (Tofwerk, Thun, Switzerland) at different voltages to determine absolute DT CCS (N2 ) values. Five POM compounds (Lindqvist TBA2 Mo6 O19; decatungstate TBA4 W10 O32; Keggin TBA3 PMo12 O40 ; TBA3 PW12 O40 and Dawson TBA6 P2 W18 O62 ) were used for the calibration of the TWIM-MS instrument (Synapt G2 HDMS, Waters, Manchester, UK) and a sixth Dawson POM, TBA9 P2 Nb3 W15 O62 , was used to compare the accuracy of the calibrations with POM or with polyalanine and dextran reference ions. RESULTS We determined 45 DT CCS (N2 ) values at 30°C or 60°C. Fourteen DT CCS (N2 ) values at 30°C were used to perform calibration of the TWIMS instrument. Better correlations were observed than when DT CCS values in helium from the literature were used. The accuracy tests on six ions of Dawson POM TBA9 P2 Nb3 W15 O62 led to relative errors below 3.1% while relative errors of 3.6% to 10.1% were observed when calibration was performed with polyalanine and dextran reference ions. CONCLUSIONS Our novel calibration strategy for determination of CCS values of multiply negatively charged ions on TWIM-MS devices based on DT CCS (N2 ) of standard POM structures covered a wider range of CCS and improved the accuracy to 2.1% relative error on average compared with 6.9% using polyalanine and dextran calibration.

Published
2018
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38. Unveiling the Active Surface Sites in Heterogeneous Titanium-Based Silicalite Epoxidation Catalysts: Input of Silanol-Functionalized Polyoxotungstates as Soluble Analogues

Author

Lise-Marie Chamoreau, Geoffroy Guillemot, Teng Zhang, Anna Proust, Céline Paris, Louis Mazaud, Institut Parisien de Chimie Moléculaire (IPCM), Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de chimie moléculaire (LCM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-École polytechnique (X), De la Molécule aux Nanos-objets : Réactivité, Interactions et Spectroscopies (MONARIS), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Edifices PolyMétalliques (E-POM), 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), 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
Titanium, 010405 organic chemistry, Chemistry, polyoxotungstate, chemistry.chemical_element, hydrogen peroxide, General Chemistry, Active surface, 010402 general chemistry, 01 natural sciences, Catalysis, 0104 chemical sciences, chemistry.chemical_compound, Silanol, Polymer chemistry, site-isolated catalysts, epoxidation, [CHIM]Chemical Sciences, Hydrogen peroxide, silanol, Tetrahydrofuran
Abstract

International audience; We report on a site-isolated model for Ti(IV) by reacting [Ti(i PrO) 4 ] with the silanol-functionalized polyoxotungstates [XW 9 O 34-x (t BuSiOH) 3 ] 3-(X= P, x=0, 1; X= Sb, x=1, 2) in tetrahydrofuran. The resulting titanium(IV) complexes [XW 9 O 34-x (t BuSiO) 3 Ti(O i Pr)] 3-(X= P, 3; X= Sb, 4) were obtained in monomeric forms both in solution and in the solid state, as proved by diffusion NMR experiments and by X-ray crystallographic analysis. Anions 3 and 4 represent 2 relevant soluble models for heterogeneous titanium silicalite epoxidation catalysts. The POM scaffolds feature slight conformational differences that influence the chemical behavior of 3 and 4 as demonstrated by their reaction with H 2 O. In the case of 3, the hydrolysis reaction of the isopropoxide ligand is only little shifted towards the formation of a monomeric [PW 9 O 34 (t BuSiO) 3 Ti(OH)] 3-(5) species [log K=-1.96], whereas 4 reacted readily with H 2 O to form a -oxo bridged dimer {[SbW 9 O 33 (t BuSiO) 3 Ti] 2 O} 6-(6). The more confined the coordination site, the more hydrophobic the metal complex. By studying the reaction of 3 and 4 with hydrogen peroxide using NMR and Raman spectroscopies, we concluded that the reaction leads to the formation of a titanium-hydroperoxide Ti-( 1-OOH) moiety, which is directly involved in the epoxidation of the allylic alcohol 3-methyl-2-buten-1-ol. The combined use of both spectroscopies also led to understanding that a shift of the acid-base equilibrium towards the formation of Ti( 2-O 2) and H 3 O + correlates with the partial hydrolysis of the phosphotungstate scaffold in 3. In that case, the release of protons also catalyzed the oxirane opening of the in situ formed epoxide, leading to an increased selectivity for 1,2,3-butane-triol. In the case of the more stable [SbW 9 O 33 (t BuSiO) 3 Ti(O i Pr)] 3-(4), the evolution to Ti( 2-O 2) peroxide was not detected by Raman spectroscopy and we performed reaction progress kinetic analysis by NMR monitoring the 3-methyl-2-buten-1-ol epoxidation in order to assess the efficiency and integrity of 4 as precatalyst.

Published
2018
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39. Modeling the Oxygen Vacancy at a Molecular Vanadium(III) Silica-Supported Catalyst

Author

Albert Solé-Daura, Céline Paris, Sébastien Blanchard, Yanling Li, Teng Zhang, Sarah Hostachy, Josep M. Poblet, Jorge J. Carbó, Geoffroy Guillemot, Anna Proust, 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), Departament de Química Física i Inorgànica, Universitat Rovira i Virgili, Edifices PolyMétalliques (E-POM), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Chimie Moléculaire de Paris Centre (FR 2769), De la Molécule aux Nanos-objets : Réactivité, Interactions et Spectroscopies (MONARIS), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Equipe de Recherche en Matériaux Moléculaires et Spectroscopies (ERMMES)

Subjects
010405 organic chemistry, Chemistry, POLE 2, Vanadium, chemistry.chemical_element, General Chemistry, 010402 general chemistry, 01 natural sciences, Biochemistry, E-POM, Catalysis, 0104 chemical sciences, chemistry.chemical_compound, Paramagnetism, Colloid and Surface Chemistry, Physical chemistry, [CHIM]Chemical Sciences, ERMMES, Partial oxidation, Singlet state, Ground state, Tetrahydrofuran, Derivative (chemistry)
Abstract

Here we report on the use of a silanol-decorated polyoxotungstate, [SbW9O33(tBuSiOH)3]3\textendash (1), as a molecular support to describe the coordination of a vanadium atom at a single-site on silica surfaces. By reacting [V(Mes)3·thf] (Mes = 2,4,6-trimethylphenyl) with 1 in tetrahydrofuran, the vanadium(III) derivative [SbW9O33(tBuSiO)3V(thf)]3\textendash (2) was obtained. Compound 2 displays the paramagnetic behavior expected for a d2-VIII high spin complex (SQUID measurements) with a triplet electronic ground state (ca. 30 kcal·mol\textendash 1 more stable than the singlet, from DFT calculations). Compound 2 proves to be a reliable model for reduced isolated-vanadium atom dispersed on silica surfaces [(\equivSi\textemdash O)3VIII(OH2)], an intermediate that is often proposed in a Mars\textendash van Krevelen type mechanism for partial oxidation of light alcohols. Oxidation of 2 under air produced the oxo-derivative [SbW9O33(tBuSiO)3VO]3\textendash (3). In compound 2, the d2-electrons are localized in degenerated d(V) orbitals, whereas in the electronically analogous bireduced-[SbW9O33(tBuSiO)3VO]5\textendash, 3·(2e), one electron is localized on d(V) orbital and the second one is delocalized on the polyoxotungstic framework, leading to a unique case of a bireduced heteropolyanion derivative with completely decoupled d1-V(IV) and d1-W(V). Our body of experimental results (EPR, magnetic measurements, spectroelectrochemical studies, Raman spectroscopy) and theoretical studies highlights (i) the role of the apical ligand coordination, i.e., thf (σ-donor) vs oxo (π-donor), in destabilizing or stabilizing the d(V) orbitals relative to the d(W) orbitals, and (ii) a geometrical distortion of the O3VO entity that causes a splitting of the degenerated orbitals and the stabilization of one d(V) orbital in the bireduced compound 3·(2e).

Published
2018
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40. Molecular Signature of Polyoxometalates in Electron Transport of Silicon-based Molecular Junctions

Author

Anna Proust, Stéphane Lenfant, Dominique Vuillaume, David Guerin, Kevin Dalla Francesca, Maxime Laurans, Florence Volatron, Guillaume Izzet, 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), Institut d’Électronique, de Microélectronique et de Nanotechnologie - UMR 8520 (IEMN), Centrale Lille-Institut supérieur de l'électronique et du numérique (ISEN)-Université de Valenciennes et du Hainaut-Cambrésis (UVHC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université Polytechnique Hauts-de-France (UPHF), Nanostructures, nanoComponents & Molecules - IEMN (NCM-IEMN), Centrale Lille-Institut supérieur de l'électronique et du numérique (ISEN)-Université de Valenciennes et du Hainaut-Cambrésis (UVHC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université Polytechnique Hauts-de-France (UPHF)-Centrale Lille-Institut supérieur de l'électronique et du numérique (ISEN)-Université de Valenciennes et du Hainaut-Cambrésis (UVHC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université Polytechnique Hauts-de-France (UPHF), 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), 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), Nanostructures, nanoComponents & Molecules - IEMN (NCM - IEMN), Université Pierre et Marie Curie - Paris 6 (UPMC)-ESPCI ParisTech-Ecole Nationale Supérieure de Chimie de Paris- Chimie ParisTech-PSL (ENSCP)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS Paris)-Université Pierre et Marie Curie - Paris 6 (UPMC)-ESPCI ParisTech-Ecole Nationale Supérieure de Chimie de Paris- Chimie ParisTech-PSL (ENSCP)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS Paris)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Institut d’Électronique, de Microélectronique et de Nanotechnologie (IEMN) - UMR 8520 (IEMN), and Centre National de la Recherche Scientifique (CNRS)-Université de Lille-Université Polytechnique Hauts-de-France (UPHF)-Ecole Centrale de Lille-Université Polytechnique Hauts-de-France (UPHF)-Institut supérieur de l'électronique et du numérique (ISEN)

Subjects
FOS: Physical sciences, 02 engineering and technology, Applied Physics (physics.app-ph), [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, Electrochemistry, 01 natural sciences, Monolayer, Mesoscale and Nanoscale Physics (cond-mat.mes-hall), Molecule, General Materials Science, Molecular orbital, [PHYS.COND]Physics [physics]/Condensed Matter [cond-mat], Physics, [PHYS]Physics [physics], Condensed Matter - Mesoscale and Nanoscale Physics, [CHIM.MATE]Chemical Sciences/Material chemistry, Physics - Applied Physics, 021001 nanoscience & nanotechnology, Electron transport chain, 0104 chemical sciences, Crystallography, Covalent bond, Electrode, Polyoxometalate, 0210 nano-technology
Abstract

International audience; Polyoxometalates (POMs) are unconventional electro-active molecules with a great potential for applications in molecular memories, providing efficient processing steps onto electrodes are available. The synthesis of the organic-inorganic polyoxometalate hybrids [PM$_{11}$O$_{39}$(Sn(C$_6$H$_4$)C$\equiv$C(C$_6$H$_4$)N$_2$)]$^{3-}$ (M = Mo, W) endowed with a remote diazonium function is reported together with their covalent immobilization onto hydrogenated n-Si(100) substrates. Electron transport measurements through the resulting densely-packed monolayers contacted with a mercury drop as a top electrode confirms their homogeneity. Adjustment of the current-voltage curves with the Simmons equation gives a mean tunnel energy barrier of 1.8 eV and 1.6 eV, for the Silicon-Molecules-Metal (SMM) junctions based on the polyoxotungstates (M = W) and polyoxomolybdates (M = Mo), respectively. This follows the trend observed in the electrochemical properties of POMs in solution, the polyoxomolybdates being easier to reduce than the polyoxotungstates, in agreement with lowest unoccupied molecular orbitals (LUMOs) of lower energy. The molecular signature of the POMs is thus clearly identifiable in the solid-state electrical properties and the unmatched diversity of POM molecular and electronic structures should offer a great modularity.

Published
2018
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41. Heteropolytungstate-decorated core-shell magnetic nanoparticles: A covalent strategy for polyoxometalate-based hybrid nanomaterials

Author

Vincent Dupuis, Aude Michel, Anna Proust, Emilie Secret, Jean-Michel Siaugue, Richard Villanneau, Ourania Makrygenni, Dalil Brouri, Institut Parisien de Chimie Moléculaire (IPCM), Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), PHysicochimie des Electrolytes et Nanosystèmes InterfaciauX (PHENIX), 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)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Laboratoire de Réactivité de Surface (LRS), Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Edifices PolyMétalliques (E-POM), and 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)

Subjects
Materials science, Nanocomposite, Nanoparticle, Nanotechnology, 02 engineering and technology, [CHIM.MATE]Chemical Sciences/Material chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Nanomaterial-based catalyst, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Nanomaterials, Biomaterials, Colloid and Surface Chemistry, Covalent bond, Polyoxometalate, Magnetic nanoparticles, 0210 nano-technology, Hybrid material
Abstract

International audience; Amino-functionalized core–shell magnetic nanoparticles have been covalently grafted with Polyoxometalates (POMs). These multifunctional nanocomposites have been obtained through the coupling of heteropolytungstate-based hybrids bearing carboxylic acid functions with aminopropyl functions that decorate the core–shell nanoparticles. The physical properties of the resulting materials have been studied by a large set of techniques. The very good nanostructuration of the POMs at the surface of the obtained nanoparticles have thus been directly observed by high-resolution transmission electronic microscopy (HR-TEM). Furthermore, the hyperthermia properties of these nanocomposites have been also considered as a function of the size of the magnetic core. Finally, the stability of these suspensions in organic media makes them particularly interesting in the frame of their processing or their potential use as nanocatalysts.

Published
2018
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43. Enhancement of photovoltaic efficiency by insertion of a polyoxometalate layer at the anode of an organic solar cell

Author

Denis Fichou, Guillaume Izzet, Anna Proust, Nicholas Barrett, Julien E. Rault, Q. Zhu, M. Alaaeddine, Ludovic Tortech, 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), Laboratoire Innovation en Chimie des Surfaces et NanoSciences (LICSEN UMR 3685), Nanosciences et Innovation pour les Matériaux, la Biomédecine et l'Energie (ex SIS2M) (NIMBE UMR 3685), Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Synchrotron SOLEIL (SSOLEIL), Centre National de la Recherche Scientifique (CNRS), Laboratoire d'Etude des NanoStructures et Imagerie de Surface (LENSIS), Service de physique de l'état condensé (SPEC - UMR3680), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay, Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire Innovation en Chimie des Surfaces et NanoSciences (LICSEN), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut Rayonnement Matière de Saclay (IRAMIS), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)

Subjects
Condensed Matter - Materials Science, Materials science, Organic solar cell, Photovoltaic system, Materials Science (cond-mat.mtrl-sci), FOS: Physical sciences, Physics - Applied Physics, Applied Physics (physics.app-ph), [CHIM.MATE]Chemical Sciences/Material chemistry, 7. Clean energy, Polymer solar cell, Anode, Indium tin oxide, Inorganic Chemistry, X-ray photoelectron spectroscopy, Chemical engineering, Polyoxometalate, Layer (electronics)
Abstract

In this article the Wells-Dawson polyoxometalate K6[P2W18O62] is grown as an interfacial layer between indium tin oxide and bulk heterojunction of poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM). The structure of the POM layers depends on the thickness and shows a highly anisotropic surface organization. The films have been characterized by atomic force microscopy and X-ray photoelectron spectroscopy (XPS) to gain insight into their macroscopic organization and better understand their electronic properties. Then, they were put at the anodic interface of a P3HT:PCBM organic solar cell and characterized on an optical bench. The photovoltaic efficiency is discussed in terms of the benefit of the polyoxometalate at the anodic interface of an organic photovoltaic cell., Comment: 7 pages, 6 figures

Published
2014
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44. Foreword

Author

Bineta Keita, Anna Proust, P. Gouzerh, Ulrich Kortz, Laboratoire de Chimie Physique D'Orsay (LCPO), Université Paris-Sud - Paris 11 (UP11)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Edifices PolyMétalliques (E-POM), Institut Parisien de Chimie Moléculaire (IPCM), 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), and 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)

Subjects
[CHIM]Chemical Sciences, General Materials Science, 02 engineering and technology, General Chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, 0210 nano-technology, Condensed Matter Physics, 01 natural sciences, Biochemistry, ComputingMilieux_MISCELLANEOUS, 0104 chemical sciences
Abstract

International audience; no abstract

Published
2013
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45. Photochromic Properties of Polyoxotungstates with Grafted Spiropyran Molecules

Author

Philippe Deniard, Lise-Marie Chamoreau, Anne Dolbecq, Khadija Hakouk, Guillaume Izzet, Houda El Bekkachi, Rémi Dessapt, Olivier Oms, Anna Proust, Arnaud Parrot, Pierre Mialane, Institut Parisien de Chimie Moléculaire (IPCM), Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), Institut Lavoisier de Versailles (ILV), Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut des Matériaux Jean Rouxel (IMN), 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)-Ecole Polytechnique de l'Université de Nantes (EPUN), Université de Nantes (UN)-Université de Nantes (UN), Université de Nantes (UN)-Université de Nantes (UN)-Ecole Polytechnique de l'Université de Nantes (EPUN), and Université de Nantes (UN)-Université de Nantes (UN)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Spiropyran, 010405 organic chemistry, Sonogashira coupling, Chromophore, 010402 general chemistry, Photochemistry, 01 natural sciences, 0104 chemical sciences, Inorganic Chemistry, chemistry.chemical_compound, Photochromism, chemistry, Covalent bond, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], Molecule, Physical and Theoretical Chemistry, Hybrid material, Derivative (chemistry)
Abstract

International audience; The first systems associating in a single molecule polyoxotungstates (POTs) and photochromic organic groups have been elaborated. Using the (TBA)4[PW11O39{Sn(C6H4I)}] precursor, two hybrid organic-inorganic species where a spiropyran derivative (SP) has been covalently grafted onto a {PW11Sn} fragment via a Sonogashira coupling have been successfully obtained. Alternatively, a complex containing a silicotungstate {PW11Si2} unit connected to two spiropyran entities has been characterized. The purity of these species has been assessed using several techniques, including 1H and 31P NMR spectroscopy, mass spectrometry, and electrochemical measurements. The optical properties of the hybrid materials have been investigated both in solution and in the solid state. These studies reveal that the grafting of SPs onto POTs does not significantly alter the photochromic behavior of the organic chromophore in solution. In contrast, these novel hybrid SP-POT materials display highly effective solid-state photochromism from neutral SP molecules initially nonphotochromic in the crystalline state. The photoresponses of the SP-POT systems in the solid state strongly depend on the nature and the number of grafted SP groups.

Published
2013
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46. Tailor-made Covalent Organic-Inorganic Polyoxometalate Hybrids: Versatile Platforms for the Elaboration of Functional Molecular Architectures

Author

Florence Volatron, Anna Proust, Guillaume Izzet, Edifices PolyMétalliques (E-POM), 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), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-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 Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), and Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Materials science, Personal account, 010405 organic chemistry, General Chemical Engineering, Nanotechnology, General Chemistry, 010402 general chemistry, 01 natural sciences, Biochemistry, 0104 chemical sciences, Artificial photosynthesis, Covalent bond, Polyoxometalate, Organic inorganic, Materials Chemistry, [CHIM]Chemical Sciences, Molecular materials, Elaboration, ComputingMilieux_MISCELLANEOUS
Abstract

Post-functionalization of organically modified polyoxometalates (POMs) is a powerful synthetic tool to devise functional building blocks for the rational elaboration of POM-based molecular materials. In this personal account we focus on iodoaryl-terminated POM platforms, describe reliable routes to the synthesis of covalent organic-inorganic POM-based hybrids and their integration into advanced molecular architectures or multi-scale assemblies as well as their immobilization onto surfaces. Valorisation of the remarkable redox properties of POMs in the fields of artificial synthesis and molecular electronic is especially considered.

Published
2017
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47. Photochromism and Dual-Color Fluorescence in a Polyoxometalate\textendashBenzospiropyran Molecular Switch

Author

Anna Proust, Arnaud Parrot, Guillaume Izzet, Stefano A. Serapian, Aurélie Jacquart, Anne Dolbecq, Aurélie Bernard, Carles Bo, Pierre Mialane, Olivier Oms, Rémi Métivier, Etienne Derat, Institut Parisien de Chimie Moléculaire (IPCM), Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), Barcelona Institute of Science and Technology (BIST), Méthodes et Application en Chimie Organique (MACO), Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), Institut Lavoisier de Versailles (ILV), Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Centre National de la Recherche Scientifique (CNRS), Edifices PolyMétalliques (E-POM), Laboratoire de Photophysique et Photochimie Supramoléculaires et Macromoléculaires (PPSM), École normale supérieure - Cachan (ENS Cachan)-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), Universitat Rovira i Virgili, Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), École normale supérieure - Cachan (ENS Cachan)-Institut de Chimie du CNRS (INC)-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), Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Cachan (ENS Cachan), and Química Física i Inorgànica

Subjects
Polioxometal·lats, POLE 2, POLE 1, Population, 02 engineering and technology, 010402 general chemistry, Photochemistry, 01 natural sciences, Catalysis, Photochromism, Density functional calculations, E-POM, fluorescence, MACO, molecular photoswitches, photochromism, POLE 1, POLE 2, Polyoxometalates, [CHIM]Chemical Sciences, polyoxometalates, education, 1433-7851, Molecular switch, education.field_of_study, 010405 organic chemistry, Chemistry, Polyoxometalates, molecular photoswitches, General Medicine, General Chemistry, Química, 021001 nanoscience & nanotechnology, photochromism, Fluorescence, E-POM, Fluorescència, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Density functional calculations, Covalent bond, Polyoxometalate, density functional calculations, fluorescence, 0210 nano-technology, MACO, Two-dimensional nuclear magnetic resonance spectroscopy, Excitation, Fisicoquímica
Abstract

The photophysical properties of a Keggin-type polyoxometalate (POM) covalently bounded to a benzospir- opyran (BSPR) unit have been investigated. These studies reveal that both closed and open forms are emissive with distinct spectral features (lem (closed form) = 530 nm, lem (open form) = 670 nm) and that the fluorescence of the BSPR unit of the hybrid is considerably enhanced compared to BSPR parent compounds. While the fluorescence excitation energy of the BSPR reference compounds (370 nm) is close to the intense absorption responsible of the photochromic character (350 nm), the fluorescence excitation of the hybrid is shifted to lower energy (400 nm), improving the population of the emissive state. Combined NOESY NMR and theoretical calculations of the closed form of the hybrid give an intimate understanding of the conformation adopted by the hybrid and show that the nitroaryl moieties of the BSPR is folded toward the POM, which should affect the electronic properties of the BSPR. &nbsp

Published
2017
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48. Charge Effect on the Formation of Polyoxometalate-Based Supramolecular Polygons Driven by Metal Coordination

Author

Madeleine Piot, Anna Proust, Laurent Bouteiller, Hélène Lavanant, Guillaume Izzet, Carlos Afonso, Sébastien Hupin, 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), Chimie Organique et Bioorganique : Réactivité et Analyse (COBRA), Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie Organique Fine (IRCOF), Université de Rouen Normandie (UNIROUEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Normandie Université (NU), Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie Organique Fine (IRCOF), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Université de Rouen Normandie (UNIROUEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), and Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)

Subjects
010405 organic chemistry, Chemistry, Electrospray ionization, Diffusion, Supramolecular chemistry, Analytical chemistry, Isothermal titration calorimetry, Nuclear magnetic resonance spectroscopy, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Inorganic Chemistry, Metal, Crystallography, chemistry.chemical_compound, visual_art, Polyoxometalate, Pyridine, visual_art.visual_art_medium, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Physical and Theoretical Chemistry
Abstract

International audience; The metal-driven self-assembly of a Keggin-based hybrid bearing two remote pyridine units was investigated. The resulting supramolecular species were identified by combination of 2D diffusion NMR spectroscopy (DOSY) and electrospray ionization mass spectrometry (ESI-MS) as a mixture of molecular triangles and squares. This behavior is different from that of the structural analogue Dawson-based hybrid displaying a higher charge, which only led to the formation of molecular triangles. This study highlights the decisive effect of the charge of the POMs in their self-assembly processes that disfavors the formation of large assemblies. An isothermal titration calorimetry (ITC) experiment confirmed the stronger binding in the case of the Keggin hybrids. A correlation between the diffusion coefficient D and the molecular mass M of the POM-based building block and its coordination oligomers was also observed. We show that the diffusion coefficient of these compounds is mainly determined by their occupied volume rather than by their shape.

Published
2017
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49. Les 40 ans de la division chimie de coordination

Author

Marvaud, Valérie, Poli, Rinaldo, Anna, Proust, 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), Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), 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), and Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
[CHIM.COOR]Chemical Sciences/Coordination chemistry
Abstract

International audience; La division Chimie de coordination a célébré son 40e anniversaire en janvier 2017. L’occasion de rappeler les différentes étapes de sa création, les précurseurs du domaine, d’évoquer les moments importants, et surtout de rendre hommage aux principaux acteurs.C’est en réunissant les témoignages des anciens présidents de la division que nous avons pu collecter les informations qui retracent quarante années d’une chimie qui a été mise à l’honneur lors de la cérémonie officielle de remise du prix Nobel à Oslo en novembre 2016.

Published
2017

50. Electron Transfer to a Phosphomolybdate Monolayer on Glassy Carbon: Ambivalent Effect of Protonation

Author

Corentin Rinfray, Catherine Combellas, Guillaume Izzet, Vitor Brasiliense, Frédéric Kanoufi, Anna Proust, Florence Volatron, Sandra Alves, Institut Parisien de Chimie Moléculaire (IPCM), 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), Interfaces, Traitements, Organisation et Dynamique des Systèmes (ITODYS (UMR_7086)), Université Paris Diderot - Paris 7 (UPD7)-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), Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), Université Pierre et Marie Curie (Paris 6), and Centre National de la Recherche Scientifique (CNRS)-Université Paris Diderot - Paris 7 (UPD7)

Subjects
Protonation, 02 engineering and technology, Glassy carbon, 010402 general chemistry, 021001 nanoscience & nanotechnology, Photochemistry, Electrochemistry, 01 natural sciences, 0104 chemical sciences, Inorganic Chemistry, chemistry.chemical_compound, Electron transfer, chemistry, Electrode, Monolayer, Trifluoroacetic acid, Organic chemistry, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, Cyclic voltammetry, 0210 nano-technology, ComputingMilieux_MISCELLANEOUS
Abstract

The polyoxomolybdate hybrid TBA3[PMo11O39{Sn(C6H4)C≡C(C6H4)N2}] K(Mo)Sn[N2(+)] was prepared through Sonogashira-type coupling between TBA4[PMo11O39{Sn(C6H4)I}] K(Mo)Sn[I] and an excess of 3,3-diethyl-1-(4-ethynylphenyl)triaz-1-ene bearing a protected diazonium function, followed by its deprotection by the addition of trifluoroacetic acid (TFA). This enlarges the family of organic-inorganic polyoxomolybdate-based hybrids, which has been far less investigated than their related polyoxotungstates. The diazonium function allows for the electrochemical grafting on glassy carbon, and the K(Mo)Sn-modified electrode was further probed by cyclic voltammetry. The PMo11Sn core was found to be highly sensitive to protonation, and five bielectronic proton-coupled electron transfer processes were detected in the presence of an excess of TFA, thus corresponding to the injection of up to 10 electrons in the potential range between 0.15 and -0.45 V/SCE. The gain observed in the thermodynamic potentials is however detrimental to the apparent kinetics of the electron transfer, which drops from 500 s(-1) in the absence of acid to 12 s(-1) in the presence of an excess of TFA.

Published
2016
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