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1. Iridium(<scp>i</scp>) complexes with bidentate NHC ligands as catalysts for dehydrogenative directed C–H silylation

Author: Romane Manguin, María Galiana-Cameo, Tanakorn Kittikool, Cécile Barthes, Jompol Thongpaen, Etienne Bancal, Sonia Mallet-Ladeira, Sirilata Yotphan, Ricardo Castarlenas, Marc Mauduit, Jean-Baptiste Sortais, Olivier Baslé, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), University of Zaragoza - Universidad de Zaragoza [Zaragoza], Laboratoire de chimie de coordination (LCC), 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)-Centre National de la Recherche Scientifique (CNRS), and Mahidol University [Bangkok]
Subjects: Materials Chemistry, Metals and Alloys, Ceramics and Composites, [CHIM]Chemical Sciences, General Chemistry, Catalysis, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials
Abstract: International audience; A series of (NHC)(cod)Ir(I) complexes bearing NHC-carboxylate ligands were efficiently synthesized and fully characterized. Their solid-state structures confirmed the bidentate coordination mode of these LX-type NHC ligands. These unprecedented iridium(I) complexes demonstrated efficient catalytic activities in dehydrogenative directed C-H silylation of arenes, and allowed for excellent ortho-selectivity control with aromatic silylating agents.
Published: 2023
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2. Reductive activation of N2 using a calcium/potassium bimetallic system supported by an extremely bulky diamide ligand

Author: Rahul Mondal, K. Yuvaraj, Thayalan Rajeshkumar, Laurent Maron, Cameron Jones, School of Chemistry, Monash University, 3800 Clayton, Victoria (Australie), Monash University [Clayton], 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), and Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)
Subjects: spectroscopy, Materials Chemistry, Metals and Alloys, Ceramics and Composites, [CHIM]Chemical Sciences, General Chemistry, nitrogen, Catalysis, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials
Abstract: An extremely bulky xanthene bridged diamide ligand ((NON)-N-TCHP = 4,5-bis(2,4,6-tricyclohexylanilido)-2,7-diethyl-9,9-dimethyl-xanthene) has been developed and used to prepare two monomeric diamido-calcium complexes [((NON)-N-TCHP)Ca(D)(n)] (D = THF, n = 2, 3; D = toluene, n = 1, 4). Reduction of 4 with 5% w/w K/KI under an N-2 atmosphere gave the first well-defined, hetero-bimetallic s-block complex of activated dinitrogen, [{K((NON)-N-TCHP)Ca}(2)(mu-eta(2):eta(2)-N-2)] 5, presumably via a transient calcium(i) intermediate.
Published: 2022
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3. Highly stable silver nanohybrid electrocatalysts for the oxygen reduction reaction

Author: Quentin Lenne, Maurice Retout, Bryan Gosselin, Gilles Bruylants, Ivan Jabin, Jonathan Hamon, Corinne Lagrost, Yann R. Leroux, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université libre de Bruxelles (ULB), Institut des Matériaux Jean Rouxel (IMN), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Nantes université - UFR des Sciences et des Techniques (Nantes univ - UFR ST), Nantes Université - pôle Sciences et technologie, Nantes Université (Nantes Univ)-Nantes Université (Nantes Univ)-Nantes Université - pôle Sciences et technologie, Nantes Université (Nantes Univ)-Nantes Université (Nantes Univ)-Nantes Université - Ecole Polytechnique de l'Université de Nantes (Nantes Univ - EPUN), and Nantes Université (Nantes Univ)-Nantes Université (Nantes Univ)
Subjects: Materials Chemistry, Metals and Alloys, Ceramics and Composites, [CHIM]Chemical Sciences, General Chemistry, Catalysis, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials
Abstract: International audience; Silver nanoparticles (AgNPs) were deliberately functionalized via aryl diazonium chemistry with a monolayer of calix[4]arenes. The resulting nanohybrids show high efficiency and high selectivity toward the ORR in alkaline media along with an exceptional durability and a high methanol tolerance.
Published: 2022
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4. Unnatural cyclodextrins can be accessed from enzyme-mediated dynamic combinatorial libraries

Author: Michel Ferreira, Sebastien Tilloy, Sophie Beeren, Dennis Larsen, Eric Monflier, Danmarks Tekniske Universitet = Technical University of Denmark (DTU), UCCS Équipe Catalyse Supramoléculaire, Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), and Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)
Subjects: Cyclodextrins, Molecular Structure, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Glucosyltransferases, Materials Chemistry, Metals and Alloys, Ceramics and Composites, [CHIM]Chemical Sciences, General Chemistry, Catalysis, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials
Abstract: International audience; Dynamic systems of cyclodextrins (CDs) enabled by a native cyclodextrin glucanotransferase (CGTase) can incorporate unnatural glucopyranose-derived building blocks, expanding the applicability of enzyme-mediated dynamic combinatorial chemistry by using synthetically modified substrates. Starting dynamic combinatorial libraries from CDs with a single 6-modified glucopyranose results in a dynamic mixture of CDs containing several modified glucopyranoses. The relative concentrations of modified α, β or γ-CDs can be controlled by the addition of templates, providing a novel way to access modified CDs.
Published: 2022
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5. Synthesis of a helicene-fused porphyrin leading to a π-extended chiral chromophore

Author: Vincent Silber, Nathalie Gruber, Marion Jean, Nicolas Vanthuyne, Romain Ruppert, Institut des Sciences Moléculaires de Marseille (ISM2), Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie de Strasbourg, and Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Porphyrins, Materials Chemistry, Metals and Alloys, Ceramics and Composites, [CHIM]Chemical Sciences, Polycyclic Compounds, Stereoisomerism, General Chemistry, Oxidation-Reduction, Catalysis, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials
Abstract: International audience; The preparation of several covalently linked [6]-heliceneporphyrins is reported. A fused [6]-helicene-porphyrin p-extended aromatic system was isolated, the enantiomers separated and the chiroptical properties determined. The oxidative cyclodehydrogenation proved to be very effective for six-membered fused helical systems, but not suited for the formation of five-membered fused systems.
Published: 2022
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6. Electronic, steric and catalytic properties of N-heterocyclic carbene rhodium(<scp>i</scp>) complexes linked to (metallo)porphyrins

Author: Ludivine Poyac, Stefano Scoditti, Xavier Dumail, Michel Granier, Sébastien Clément, Rafael Gramage-Doria, Charles H. Devillers, Sébastien Richeter, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), Università della Calabria [Arcavacata di Rende] (Unical), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie Moléculaire de l'Université de Bourgogne [Dijon] (ICMUB), Université de Bourgogne (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and ANR-19-CE07-0039,REMOTCAT,Fonctionalisation 'remote' des molecules par catalyse supramoleculaire(2019)
Subjects: Porphyrins, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Metals and Alloys, [CHIM.CATA]Chemical Sciences/Catalysis, General Chemistry, Catalysis, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Heterocyclic Compounds, Materials Chemistry, Ceramics and Composites, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Rhodium, Electronics
Abstract: International audience; Electronic and steric properties of NHC ligands functionalized with porphyrins were investigated. When porphyrins are used as NHCwingtips, nickel(II) in the macrocyle significantly improves the catalytic activity of the neighbouring NHC-Rh(I) complex in the conjugate addition of phenylboronic acid to cyclohexen-2-one.
Published: 2022
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7. Chemical exchange of labile protons by deuterium enables selective detection of pharmaceuticals in solid formulations

Author: Claire Welton, Parth Raval, Julien Trébosc, G. N. Manjunatha Reddy, Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Institut Michel Eugène Chevreul - FR 2638 (IMEC), Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), and European Project: 795091,H2020,H2020-MSCA-IF-2017,ZEOCATALYST(2019)
Subjects: Dopamine, Metals and Alloys, [CHIM.THER]Chemical Sciences/Medicinal Chemistry, General Chemistry, [SDV.SP]Life Sciences [q-bio]/Pharmaceutical sciences, Deuterium, Catalysis, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Pharmaceutical Preparations, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Materials Chemistry, Ceramics and Composites, Amino Acids, Protons
Abstract: International audience; Chemically assisted swapping of labile protons by deuterons is presented for amino acids, polysaccharides, pharmaceutical compounds, and their solid formulations. Solid-state packing interactions in these compounds are elucidated by 1H–2H isotope correlation NMR spectroscopy (iCOSY). A minuscule concentration of dopamine, 5 wt% or ∼100 μg, in a solid formulation can be detected by 2H NMR at 28.2 T (1H, 1200 MHz) in under a minute.
Published: 2022
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8. Reductive depolymerization of polyesters and polycarbonates with hydroboranes by using a lanthanum(<scp>iii</scp>) tris(amide) catalyst

Author: Marie Kobylarski, Jean-Claude Berthet, Thibault Cantat, Laboratoire de Chimie Moléculaire et de Catalyse pour l'Energie (ex LCCEF) (LCMCE), 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), Fondation Louis D.–Institut de France, European Project: ERC CoG n°818260 ,ReNewHydrides, ICGC, IUPAC, Palacin, Serge, and Renewable Hydride Donors and Their Utilization in Catalytic Reduction and Deoxygenation Reactions - ReNewHydrides - ERC CoG n°818260 - INCOMING
Subjects: f-element, Polyesters, Chemical depolymerization, Plastic, Catalysis, Polymerization, Coordination Complexes, Lanthanum, Hydroboration, Materials Chemistry, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Boranes, [CHIM.MATE] Chemical Sciences/Material chemistry, Polycarboxylate Cement, Molecular Structure, Metals and Alloys, [CHIM.CATA] Chemical Sciences/Catalysis, [CHIM.MATE]Chemical Sciences/Material chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, General Chemistry, [CHIM.COOR] Chemical Sciences/Coordination chemistry, Amides, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Ceramics and Composites, Oxidation-Reduction
Abstract: International audience; The worldwide massive production of plastics (368 Mt per year) and the poor recycling rate of wastes materials make them a scourge for the environmental. Waste storage in landfills and waste incineration are not sustainable solutions, as well as the mechanical recycling which gradually degrades the physical properties of plastic polymers. Chemical recycling, which is the depolymerization of materials into valuable monomers or chemicals, seems to be an appealing route for the future. Currently, well-known solvolysis processes catalyzed by bases, acids and ionic liquids enable the depolymerization of polymers by hydrolysis, aminolysis or transesterification reactions. They offer the recovery of pure monomers useful for the production of new virgin plastics. Recently, the reductive depolymerization processes have appeared as alternative approaches to access new value added products from plastics. The goal is to develop catalytic systems able to selectively cut and reduce polarized bonds (carbon-oxygen and/or carbon-nitrogen) of the polymers to obtain the corresponding monomers (alcohols, amines or hydrocarbons). Such reductive deconstruction methods are scarce and are all based on the use of H$_2$ or hydrosilanes as reductants. The catalytic hydrogenolysis of oxygenated and nitrogenated polymers (polyesters, polyamines and polyurethanes) was reported with Ru(II) and Ir(III) catalysts under high pressures and temperatures, whereas their catalytic hydrosilylations could take place under milder conditions with metal-based catalysts (Ir(III), Zn(II), Mo(VI)) or organocatalysts ([Ph$_3$C][B(C$_6$F$_5$)$_4$] and B(C$_6$F$_5$)$_3$). Hydroboranes as reductants could offer distinct reactivity and selectivity due to their higher hydride donor ability than hydrosilanes and an additional pronounced Lewis acidity. Inspired by the work of T. J. Marks et al., on the reduction of esters, we considered La[N(SiMe$_3$)$_2$]$_3$ as a 4f-catalyst and the pinalcolborane as a hydride donor, for the reductive depolymerization of a wide range of polyesters and polycarbonates.
Published: 2022
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9. Enhancement of photocurrent by incorporation of Preyssler type polyoxometalate protected nanoparticles in polyporphyrin films

Author: Laurent Ruhlmann, Yiming Liang, Petra Hellwig, Helen Ibrahim, Antoine Bonnefont, Zhaohui Huo, Michel Goldmann, Yaokang Lv, Frederic Melin, Vasilica Badets, Corinne Boudon, Institut de Chimie de Strasbourg, Centre National de la Recherche Scientifique (CNRS)-Université Louis Pasteur - Strasbourg I-Institut de Chimie du CNRS (INC), Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Chimie de la matière complexe (CMC), and Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Photocurrent, Materials science, 010405 organic chemistry, Metals and Alloys, Cationic polymerization, Nanoparticle, General Chemistry, 010402 general chemistry, 01 natural sciences, Catalysis, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Chemical engineering, Polyoxometalate, Materials Chemistry, Ceramics and Composites, Copolymer, Electrostatic interaction
Abstract: The introduction of nanoparticles (MNPs) at the surface of cationic poly-porphyrin films, obtained by electrostatic interaction between the bis-porphyrin copolymer and the Preyssler type polyoxometalate P5W30@MNPs, enhances the photocurrent (up to 2.5-3 times greater as a function of the used nanoparticle).
Published: 2021
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10. Modulating alkene reactivity from oxygenation to halogenation via electrochemical O2 activation by Mn porphyrin

Author: Elodie Anxolabéhère-Mallart, Claire Fave, Frédéric Banse, Nikolaos Kostopoulos, Laboratoire d'Electrochimie Moléculaire (LEM (UMR_7591)), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Paris (UP), Institut de Chimie Moléculaire et des Matériaux d'Orsay (ICMMO), and Institut de Chimie du CNRS (INC)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)
Subjects: 010402 general chemistry, Photochemistry, 01 natural sciences, Catalysis, Benzoic anhydride, chemistry.chemical_compound, Cyclooctene, Materials Chemistry, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Reactivity (chemistry), chemistry.chemical_classification, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Chemistry, Alkene, Metals and Alloys, Halogenation, [CHIM.CATA]Chemical Sciences/Catalysis, General Chemistry, Porphyrin, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Ceramics and Composites, Cyclic voltammetry
Abstract: International audience; Oxidation of organic substrates is achieved in nature under mild conditions thanks to metalloenzymes but remains a challenge for chemists. Herein we show by UV-Vis spectroelectrochemistry that when MnIIITPPCl is electrochemically reduced to MnII in CH2Cl2 under O2, a MnIIO2˙ species is generated. Benzoic anhydride reacts with the latter triggering a catalytic current in cyclic voltammetry. Electrolysis on the catalytic wave in the presence of cyclooctene leads to its oxygenation or halogenation depending on the axial ligand present as reported here for the first time.
Published: 2021
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11. A chiral thiourea and a phosphazene for fast and stereoselective organocatalytic ring-opening-polymerization of racemic lactide

Author: Mohamed Samir Zaky, Olivier Coulembier, Anne-Laure Wirotius, Daniel Taton, Gilles Guichard, Team 1 LCPO : Polymerization Catalyses & Engineering, Laboratoire de Chimie des Polymères Organiques (LCPO), Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC), Centre d'Innovation et de Recherche en Matériaux Polymères (CIRMAP), Université de Mons (UMons), Chimie et Biologie des Membranes et des Nanoobjets (CBMN), and École Nationale d'Ingénieurs des Travaux Agricoles - Bordeaux (ENITAB)-Institut de Chimie du CNRS (INC)-Université de Bordeaux (UB)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Lactide, 010405 organic chemistry, Metals and Alloys, [CHIM.CATA]Chemical Sciences/Catalysis, General Chemistry, 010402 general chemistry, 01 natural sciences, Combinatorial chemistry, Ring-opening polymerization, Catalysis, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, chemistry.chemical_compound, [CHIM.POLY]Chemical Sciences/Polymers, Monomer, chemistry, Thiourea, Polymerization, Organocatalysis, Tacticity, Materials Chemistry, Ceramics and Composites, Phosphazene
Abstract: International audience; Control of stereoregularity is inherent to precision polymerization chemistry for the development of functional materials. A prototypal example of this strategy is the ring-opening polymerization (ROP) of racemic lactide (rac-LA), a bio-sourced monomer. Despite significant advances in organocatalysis, stereoselective ROP of rac-LA employing chiral organocatalysts remains unexplored. Here we tackle that challenge by resorting to Takemoto's catalyst, a chiral aminothiourea, in the presence of a phosphazene base. This chiral binary organocatalytic system allows for fast, chemo- and stereoselective ROP of rac-LA at room temperature, yielding highly isotactic, semi-crystalline and metal-free polylactide, with a melting temperature as high as 187 °C.
Published: 2021
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12. Redox-induced reversible P–P coupling in a uranium complex

Author: Xiong Sun, Laurent Maron, Yue Zhao, Wei Fang, Congqing Zhu, Ambre Carpentier, Nanjing Normal Univ, Key Lab Virtual Geog Environm, Minist Educ, Nanjing 210023, Peoples R China, 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), National Natural Science Foundation of China [21772088, 91961116], Programs for high-level entrepreneurial and innovative talents introduction of Jiangsu Province, Humboldt Foundation, and Chinese Academy of Science
Subjects: Denticity, Ligand, Metals and Alloys, chemistry.chemical_element, General Chemistry, Uranium, Redox, Catalysis, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Coupling (electronics), Crystallography, chemistry, Materials Chemistry, Ceramics and Composites, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph]
Abstract: International audience; A synthesized redox-active multidentate N-P ligand reacted with UCl4 in the presence of KHMDS or (BuLi)-Bu-n, where two novel U(iv) complexes with or without P-P coupling were formed, respectively. The reversible P-P coupling in these complexes was observed in redox-induced reactions.
Published: 2021
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13. A high dimensional oxysulfide built from large iron-based clusters with partial charge-ordering

Author: Angel M. Arevalo-Lopez, Houria Kabbour, Batoul Almoussawi, Pardis Simon, Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Centrale Lille Institut (CLIL)-Université d'Artois (UA)-Centrale Lille-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Lille, Université de Lille, CNRS, Centrale Lille, ENSCL, Univ. Artois, Unité de Catalyse et Chimie du Solide - UMR 8181 [UCCS], and Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)
Subjects: Spin glass, Materials science, Structural type, Metals and Alloys, 02 engineering and technology, General Chemistry, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Catalysis, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Crystallography, Partial charge, Octahedron, Iron based, [CHIM.CRIS]Chemical Sciences/Cristallography, Materials Chemistry, Ceramics and Composites, Tetrahedron, 0210 nano-technology
Abstract: International audience; Herein we report the original Ba10Fe7.75Zn5.25S18Si3O12 oxysulfide which crystallizes in a new structural type. Contrary to the usual oxychalcogenides, it crystallizes with a non-centrosymmetric 3D spatial network structure built from large magnetic clusters consisting of twelve (Fe2+/3+/Zn)S3O tetrahedra decorating a central Fe2+S6 octahedron and exhibiting a spin glass state
Published: 2021
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14. The Fischer–Tropsch reaction in the aqueous phase over rhodium catalysts: a promising route to selective synthesis and separation of oxygenates and hydrocarbons

Author: Alan J. Barrios, Vitaly V. Ordomsky, Andrei Y. Khodakov, Nataliya E. Borisova, Aleksandra S. Peregudova, Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Centrale Lille Institut (CLIL)-Université d'Artois (UA)-Centrale Lille-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Lille, Université d'Artois (UA)-Centrale Lille-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Lille, Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), and ANR-16-CE06-0013,NANO4FuT,Synthèse des carburants alternatifs et des molécules plateforme sur nanoréacteurs(2016)
Subjects: chemistry.chemical_element, Alcohol, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Catalysis, Rhodium, Metal, chemistry.chemical_compound, Materials Chemistry, [CHIM]Chemical Sciences, ComputingMilieux_MISCELLANEOUS, Oxygenate, Metals and Alloys, Aqueous two-phase system, Fischer–Tropsch process, [CHIM.CATA]Chemical Sciences/Catalysis, General Chemistry, 021001 nanoscience & nanotechnology, Combinatorial chemistry, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, chemistry, visual_art, Ceramics and Composites, visual_art.visual_art_medium, 0210 nano-technology, Selectivity
Abstract: In the present communication, we uncovered the aqueous phase Fischer-Tropsch reaction over rhodium catalysts. The reaction results in the synthesis and consecutive separation of hydrocarbons and oxygenates into two phases. Use of a rhodium Schiff base complex as a precursor for catalyst preparation allows efficient control of the Rh metal nanoparticle size distribution and leads to higher alcohol selectivity.
Published: 2020
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15. A transient lanthanum phosphinidene complex

Author: Stephan Hohloch, Laurent Maron, Roland Schoch, Fabian A. Watt, Karl N. McCabe, University of Paderborn, 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)-Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), and Universität Innsbruck [Innsbruck]
Subjects: Reaction mechanism, Metals and Alloys, chemistry.chemical_element, General Chemistry, Catalysis, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Crystallography, Deprotonation, chemistry, Phosphinidene, Materials Chemistry, Ceramics and Composites, Lanthanum, Thermal stability, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph]
Abstract: Deprotonation of the terminal phosphido complex (PN)2La(PHMes) (1) results in the C-H-activation of one of the PN ligands, formally retaining the PHMes group. The reaction mechanism and the possible involvement of the transient phosphinidene complex 2 are investigated by theoretical and chemical means including a deuteration experiment employing (PN)2La(PDMes) (1-d). Furthermore, the thermal stability of product [K(2.2.2-cryptand)][(PN)(PNcyclo)La(PHMes)] (3b) is examined, giving the diphosphido complex [K(2.2.2-cryptand)][(PN)2La(P2Mes2)] (6).
Published: 2020
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16. How trimerization of CTR1 N-terminal model peptides tunes Cu-binding and redox-chemistry

Author: Thibaut Galler, Vincent Lebrun, Nina E. Wezynfeld, Peter Faller, Laurent Raibaut, Institut de Chimie de Strasbourg, Centre National de la Recherche Scientifique (CNRS)-Université Louis Pasteur - Strasbourg I-Institut de Chimie du CNRS (INC), and Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)
Subjects: Models, Molecular, Stereochemistry, Copper metabolism, Peptide, 010402 general chemistry, 01 natural sciences, Redox, Catalysis, Materials Chemistry, Humans, Molecule, Reactivity (chemistry), Binding site, Copper Transporter 1, chemistry.chemical_classification, Binding Sites, Molecular Structure, 010405 organic chemistry, COPPER TRANSPORTER 1, fungi, Metals and Alloys, Oxidation reduction, General Chemistry, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, chemistry, Ceramics and Composites, [CHIM.OTHE]Chemical Sciences/Other, Oxidation-Reduction, Copper
Abstract: Employing peptide-based models of copper transporter 1 (CTR1), we show that the trimeric arrangement of its N-terminus tunes its reactivity with Cu, promoting Cu(ii) reduction and stabilizing Cu(i). Hence, the employed multimeric models of CTR1 provide an important contribution to studies on early steps of Cu uptake by cells.
Published: 2020
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17. Exploiting hexafluoroisopropanol (HFIP) in Lewis and Brønsted acid-catalyzed reactions

Author: David Lebœuf, Vincent Gandon, Valentyn Pozhydaiev, Joseph Moran, Martin Power, Université de Strasbourg (UNISTRA), Institut de Science et d'ingénierie supramoléculaires (ISIS), Réseau nanophotonique et optique, Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA), Université Paris-Saclay, Institut de Chimie Moléculaire et des Matériaux d'Orsay (ICMMO), Institut de Chimie du CNRS (INC)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), Leboeuf, David, Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, and Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)
Subjects: [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Chemistry, Metals and Alloys, Cationic polymerization, General Chemistry, [CHIM.ORGA] Chemical Sciences/Organic chemistry, 010402 general chemistry, 01 natural sciences, Chemical reaction, Combinatorial chemistry, Catalysis, 3. Good health, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Solvent, Acid catalysis, Nucleophile, Materials Chemistry, Ceramics and Composites, Brønsted–Lowry acid–base theory
Abstract: International audience; Hexafluoroisopropanol (HFIP) is a solvent with unique properties that has recently gained attention for promoting a wide range of challenging chemical reactions. It was initially believed that HFIP was almost exclusively involved in the stabilization of cationic intermediates, owing to its high polarity and low nucleophilicity. However, in many cases, the mechanism of action of HFIP appears to be more complex. Recent findings reveal that many Lewis and Brønsted acid-catalyzed transformations conducted in HFIP additionally involve cooperation between catalyst and HFIP hydrogen-bond clusters, akin to Lewis-or Brønsted acid-assisted-Brønsted acid catalysis. This feature article showcases the remarkable versatility of HFIP in Lewis and Brønsted acid-catalyzed reactions, with an emphasis on examples yielding mechanistic insight.
Published: 2020
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18. Accurate measurement of effective Li–Li scalar coupling constants: the NMR missing link for alkyllithium aggregates

Author: Anne Harrison-Marchand, Jacques Maddaluno, Matthieu Hedouin, Hassan Oulyadi, Université de Rouen Normandie (UNIROUEN), Normandie Université (NU), 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), and 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)
Subjects: chemistry.chemical_classification, Coupling constant, Steric effects, Work (thermodynamics), Materials science, 010405 organic chemistry, Metals and Alloys, Solvation, General Chemistry, Link (geometry), 010402 general chemistry, 01 natural sciences, Catalysis, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Scalar coupling, chemistry, Chemical physics, Materials Chemistry, Ceramics and Composites, [CHIM]Chemical Sciences, Alkyl
Abstract: International audience; Scalar coupling in organolithium systems can provide access to useful structural and dynamic informations. In this work, we propose a robust method for the accurate measurement of the effective 2 J Li-Li coupling constant in tetramerics alkyllithium aggregates. This crucial information, unavalaible to date, gives a simple access to various structural factors, including the dynamics, solvation and the operative steric hindrance of alkyl chains.
Published: 2020
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19. Manganese and rhenium-catalyzed selective reduction of esters to aldehydes with hydrosilanes

Author: Ruqaya Buhaibeh, Yves Canac, Duo Wei, Jean-Baptiste Sortais, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Laboratoire de chimie 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), 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 Universitaire de France (IUF), Ministère de l'Education nationale, de l’Enseignement supérieur et de la Recherche (M.E.N.E.S.R.), Université de Rennes 1, Institut Universitaire de France, Centre National de la Recherche Scientifique, Université Toulouse III - Paul Sabatier, Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut 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), and Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)
Subjects: chemistry.chemical_classification, Silylation, 010405 organic chemistry, Metals and Alloys, chemistry.chemical_element, General Chemistry, Manganese, Rhenium, 010402 general chemistry, 01 natural sciences, Catalysis, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Hydrolysis, chemistry.chemical_compound, chemistry, Materials Chemistry, Ceramics and Composites, [CHIM]Chemical Sciences, Organic chemistry, Selective reduction, Triethylsilane, Alkyl
Abstract: International audience; The selective reduction of esters to aldehydes, via the formation of stable alkyl silyl acetals, was, for the first time, achieved with both manganese, -Mn(CO)- and rhenium -Re(CO)- catalysts in the presence of triethylsilane as reductant. These two methods provide a direct access to a large variety of aliphatic and aromatic alkyl silyl acetals (30 examples) and to the corresponding aldehydes (13 examples) upon hydrolysis. The reactions proceeded in excellent yields and high selectivity at room temperature under photo-irradiation conditions (LED, 365 nm, 40 W, 9 h).
Published: 2020
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20. Near perfect head-to-head selectivity on the supramolecular photocyclodimerisation of 2-anthracenecarboxylate with self-organised gemini surfactant bilayers

Author: Wijak Yospanya, Takehiko Wada, Masaki Nishijima, Thierry Buffeteau, Emilie Pouget, Yasuyuki Araki, Reiko Oda, Chimie et Biologie des Membranes et des Nanoobjets (CBMN), École Nationale d'Ingénieurs des Travaux Agricoles - Bordeaux (ENITAB)-Institut de Chimie du CNRS (INC)-Université de Bordeaux (UB)-Centre National de la Recherche Scientifique (CNRS), Tohoku University [Sendai], Institut des Sciences Moléculaires (ISM), and Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Materials science, 010405 organic chemistry, Head to head, Metals and Alloys, Supramolecular chemistry, Regioselectivity, [CHIM.MATE]Chemical Sciences/Material chemistry, General Chemistry, 010402 general chemistry, 01 natural sciences, Catalysis, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Crystallography, Template, Pulmonary surfactant, 13. Climate action, 2-anthracenecarboxylate, Materials Chemistry, Ceramics and Composites, [CHIM.OTHE]Chemical Sciences/Other, Selectivity
Abstract: International audience; Silicificated self-organised crystalline bilayers of gemini surfactants were used as reaction templates for supramolecular regioselective [4+4] photocyclodimerisation of 2-anthracenecarboxylate in water. Near perfect head-to-head cyclodimers selectivity, up to 97% at room temperature was achieved with accelerated dimerisation. Ever since the first report in 1867, 1-3 the [4+4] photocyclodimerisation of anthracene and its derivatives has attracted much attention due to the unique structure and properties of the photocyclodimers obtained, and has been employed indeed as a key motif in energy storage and photoreversible devices. 4-8 However, controlling regio-and enantioselectivities of the photocyclodimerisation of anthracene derivatives, such as 2anthracenecarboxylate (AC) (Scheme 1), is a challenge, which has driven researchers to the use of supramolecular approach, 9,10 using cyclodextrins, 11-14 proteins, 15,16 molecular templates, 17-21 molecular cages, 20-22 twisted self-associated templates, 18 organogels, 23 and helical metal nanostructures 24 as hosts and templates. Most of the reported systems, however, require the multi-step synthesis of host/template, the modification of guest substrate and/or the irradiation in organic media at low temperature. From the Sustainable Development Goals (SDGs) point of view, a readily accessible, spontaneously self-organisable, operative under ambient conditions, yet biodegradable host/template is advocated, while a three-dimensionally well-defined, appropriately functionalised, structurally robust host/template is essential for directing the stereochemical course of photoreaction to desired product(s). Upon photoirradiation in aqueous media, AC form antiand syn-isomeric head-to-tail (HT) cyclodimers (ACD1 and ACD 2) and head-to-head (HH) cyclodimers (ACD 3 and ACD 4) in a 4:1 ratio (Table 1, entry 1) for steric and electrostatic reasons. Possessing two functional groups on the same side of molecule, the HH cyclodimers are structurally attractive as building blocks for functional devices and materials. 25,26 Wolff et al. succeeded to increase the HH/HT ratio of the photo-cyclodimerisation of 9-substituted anthracenes by executing the reaction in cationic and anionic micelles to gain modestly enhanced HH/HT ratios of 0.62-0.76, 27,28 for which the flexible micelle shell would be responsible for the limited value of HH/HT ratios.
Published: 2020
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21. A straightforward synthesis of a new family of molecules: 2,5,8-trialkoxyheptazines. Application to photoredox catalyzed transformations

Author: Tuan Le, Clémence Allain, Géraldine Masson, Laurent Galmiche, Pierre Audebert, Photophysique et Photochimie Supramoléculaires et Macromoléculaires (PPSM), Institut de Chimie du CNRS (INC)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Ecole Normale Supérieure Paris-Saclay (ENS Paris Saclay), Institut de Chimie des Substances Naturelles (ICSN), Institut de Chimie du CNRS (INC)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), XLIM (XLIM), and Université de Limoges (UNILIM)-Centre National de la Recherche Scientifique (CNRS)
Subjects: [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Chemistry, Band gap, education, Metals and Alloys, General Chemistry, 010402 general chemistry, Electrochemistry, 01 natural sciences, Combinatorial chemistry, Catalysis, 0104 chemical sciences, 3. Good health, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Reduction (complexity), Catalytic oxidation, Materials Chemistry, Ceramics and Composites, [CHIM]Chemical Sciences, Molecule
Abstract: We have prepared several 2,5,8-trialkoxyheptazines starting from the soluble precursor 2,5,8-tris(3,5-diethylpyrazolyl)-heptazine. We present their synthesis along with their promising spectroscopic and electrochemical properties, which demonstrate large band gaps and high reduction potentials altogether. Subsequently, we provide a short assessment of the promising ability of one of these molecules to perform catalytic oxidation test-reactions.
Published: 2020
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22. Formation of highly stable multinuclear AgnSnclusters in zinc fingers disrupts their structure and function

Author: Aurélien Deniaud, Manuel David Peris-Díaz, Wojciech Bal, Michal Dadlez, Dawid Płonka, Alexander Moysa, Artur Krężel, Katarzyna Kluska, Department of Chemical Biology, Faculty of Biotechnology, Institute of Biochemistry and Biophysics, Polish Academy of Sciences, Biologie des Métaux (BioMet ), 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), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA)
Subjects: Zinc finger, chemistry.chemical_classification, 0303 health sciences, Conformational change, Chemistry, Biomolecule, Metals and Alloys, General Chemistry, 010402 general chemistry, 01 natural sciences, Catalysis, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Structure and function, 03 medical and health sciences, Crystallography, Materials Chemistry, Ceramics and Composites, Cluster (physics), Transcriptional regulation, [CHIM]Chemical Sciences, [SDV.BBM.BC]Life Sciences [q-bio]/Biochemistry, Molecular Biology/Biochemistry [q-bio.BM], 030304 developmental biology
Abstract: International audience; Silver (Ag(I)) binding to consensus zinc fingers (ZFs) causes Zn(II) release inducing a gradual disruption of the hydrophobic core, followed by an overall conformational change and formation of highly stable AgnSn clusters. A compact eight-membered Ag4S4 structure formed by a CCCC ZF is the first cluster example reported for a single biological molecule. Ag(I)-induced conformational changes of ZFs can, as a consequence, affect transcriptional regulation and other cellular processes.
Published: 2020
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23. A versatile strategy to synthesize N-methyl-anthranilic acid-labelled glycoprobes for fluorescence-based screening assays

Author: Anne Robert, Sandrine Gulberti, Jean-Claude Jacquinet, Jean-Baptiste Vincourt, Chrystel Lopin-Bon, Nick Ramalanjaona, Mohamed Ouzzine, Isabelle Bertin-Jung, Sylvie Fournel-Gigleux, Catherine Bui, Ingénierie Moléculaire et Physiopathologie Articulaire (IMoPA), Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie Organique et Analytique (ICOA), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université d'Orléans (UO)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Institut National de la Santé et de la Recherche Médicale (INSERM)
Subjects: Anomer, 010405 organic chemistry, [SDV]Life Sciences [q-bio], Metals and Alloys, General Chemistry, 010402 general chemistry, 01 natural sciences, Combinatorial chemistry, Fluorescence, Catalysis, 0104 chemical sciences, 3. Good health, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, chemistry.chemical_compound, chemistry, Materials Chemistry, Ceramics and Composites, Anthranilic acid, [CHIM]Chemical Sciences, ComputingMilieux_MISCELLANEOUS
Abstract: Here we propose a general strategy to label carbohydrates with N-methyl-anthranilic acid at the anomeric position. Through two examples, we demonstrate that the generated glycoprobes are suitable for fluorescence-based binding/competition assays. Our approach is expected to readily generate series of glycoprobes dedicated to screening assays for the discovery of drugs targeting carbohydrate–protein interactions.
Published: 2020
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24. Cost-efficient and user-friendly 17 O/ 18 O labeling procedures of fatty acids using mechanochemistry

Author: Charlyn Fabra, Aurélien Lebrun, Marie Hubert-Roux, Isabelle Schmitz-Afonso, Dorothée Berthomieu, Jessica Špačková, Danielle Laurencin, Thomas-Xavier Métro, Guillaume Cazals, Ieva Goldberga, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Centre National de la Recherche Scientifique (CNRS), Université de Montpellier (UM), Institut des Biomolécules Max Mousseron [Pôle Chimie Balard] (IBMM), 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), 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), and Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)
Subjects: Carboxylic acid, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Catalysis, Hydrolysis, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Mechanochemistry, Materials Chemistry, Organic chemistry, chemistry.chemical_classification, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Chemistry, Metals and Alloys, General Chemistry, 021001 nanoscience & nanotechnology, 0104 chemical sciences, 3. Good health, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Oxygen atom, Docosahexaenoic acid, Ceramics and Composites, 0210 nano-technology, Saponification, Polyunsaturated fatty acid
Abstract: Two mechanochemical procedures for 17O/18O-isotope labeling of fatty acids are reported: a carboxylic acid activation/hydrolysis approach and a saponification approach. The latter route allowed first-time enrichment of important polyunsaturated fatty acids (PUFAs) including docosahexaenoic acid (DHA). Overall, a total of 9 pure labeled products were isolated in high yields (≥80%) and with high enrichment levels (≥37% average labeling of C=O and C-OH carboxylic oxygen atoms), under mild conditions, and in short time (
Published: 2021
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25. Unexplored reactivity of (Sn)2− oligomers with transition metals in low-temperature solid-state reactions

Author: Benoit Corraze, Sylvian Cadars, Elodie Grange, Shunsuke Sasaki, Catherine Guillot-Deudon, Maria Teresa Caldes, Stéphane Jobic, Mélanie Lesault, Laurent Cario, Etienne Janod, 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), Conditions Extrêmes et Matériaux : Haute Température et Irradiation (CEMHTI), and Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université d'Orléans (UO)
Subjects: Materials science, Solid-state, FOS: Physical sciences, chemistry.chemical_element, Electron, 010402 general chemistry, 01 natural sciences, Catalysis, Soft chemistry, Metal, Transition metal, Materials Chemistry, Reactivity (chemistry), ComputingMilieux_MISCELLANEOUS, Condensed Matter - Materials Science, 010405 organic chemistry, Metals and Alloys, Materials Science (cond-mat.mtrl-sci), General Chemistry, Antibonding molecular orbital, Sulfur, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Crystallography, chemistry, visual_art, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], Ceramics and Composites, visual_art.visual_art_medium
Abstract: Chalcogenides (Q = S, Se, Te), one of the most important family of materials in solid-state chemistry, differ from oxides by their ability to form covalently-bonded (Qn)2- oligomers. Each chalcogen atom within such entity fulfills the octet rule by sharing electrons with other chalcogen atoms but some antibonding levels are vacant. This makes these oligomers particularly suited for redox reactions in solid state, namely towards elemental metals with a low redox potential that may be oxidized. We recently used this strategy to design, at low temperature and in an orientated manner, materials with 2D infinite layers through the topochemical insertion of copper into preformed precursors containing (S2)2- and/or (Se2)2- dimers (i.e. La2O2S2, Ba2F2S2 and LaSe2). Herein we extend the validity of the concept to the redox activity of (S2)2- and (S3)2- oligomers towards 3d transition metal elements (Cu, Ni, Fe) and highlight the strong relationship between the structures of the precursors, BaS2 and BaS3, and the products, BaCu2S2, BaCu4S3, BaNiS2 and BaFe2S3. Clearly, beyond the natural interest for the chemical reactivity of oligomers to generate compounds, this soft chemistry route may conduct to the rational conception of materials with a predicted crystal structure.
Published: 2019
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26. Combining sol–gel and microfluidics processes for the synthesis of protein-containing hybrid microgels

Author: Jean Martinez, Mathieu Lions, Jean-Marie Devoisselle, Gilles Subra, Ahmad Mehdi, Corine Tourné-Péteilh, Baptiste Robin, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Institut Galien Paris-Sud (IGPS), Université Paris-Sud - Paris 11 (UP11)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), Institut des Biomolécules Max Mousseron [Pôle Chimie Balard] (IBMM), and 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)
Subjects: Surface Properties, Microfluidics, Biocompatible Materials, Polyethylene glycol, 010402 general chemistry, 01 natural sciences, Catalysis, Polyethylene Glycols, chemistry.chemical_compound, Materials Chemistry, Animals, Molecule, Particle Size, ComputingMilieux_MISCELLANEOUS, Sol-gel, Molecular Structure, 010405 organic chemistry, Metals and Alloys, Model protein, Hydrogels, Serum Albumin, Bovine, [CHIM.MATE]Chemical Sciences/Material chemistry, General Chemistry, Biocompatible material, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Chemical engineering, chemistry, Self-healing hydrogels, Ceramics and Composites, Cattle, Particle size, Gels
Abstract: Biocompatible chemical cross-linked hybrid polyethylene glycol-based hydrogels were obtained from a sol-gel process using bis-silylated molecular precursors in biocompatible conditions. This soft procedure (pH = 7.4, at 25 °C), allows the production of microgels by microfluidics and easy encapsulation of a model protein (Bovin Serum Albumine, BSA).
Published: 2019
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27. Monomeric thorium dihydrido complexes: versatile precursors to actinide metallacycles

Author: Laurent Maron, Iker del Rosal, Yang Wang, Guorui Qin, Jianhua Cheng, Xianghui Shi, Shanghai Institute of Materia Medica - Chinese Academy of Sciences [Shanghai], University of Chinese Academy of Sciences [Beijing] (UCAS), Institute of Computing Technology Chinese Academy of Sciences, 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)-Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), National Natural Science Foundation of China [21672202], and HPC's CALcul en Midi-Pyrenees (CALMIP-EOS grant) [1415]
Subjects: Addition reaction, 010405 organic chemistry, Metals and Alloys, Thorium, chemistry.chemical_element, General Chemistry, Actinide, 010402 general chemistry, 01 natural sciences, Medicinal chemistry, Catalysis, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, chemistry.chemical_compound, Monomer, chemistry, Materials Chemistry, Ceramics and Composites, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph]
Abstract: International audience; The monomeric actinide dihydrido complex [(Cp-Ar*)(Cp*)ThH2(THF)] (2) bearing the super-bulky penta-arylcyclopentadienyl (Cp-Ar* = C5Ar*(5), Ar* = 3,5-Bu-t(2)-C6H3) and pentamethylcyclopentadienyl (Cp* = C5Me5) ligands was obtained for the first time. Complex 2 underwent unique Th-H addition reactions with various unsaturated compounds to afford the corresponding five-membered metallacycles, including the first example of actinide metallacyclopentyne [(Cp-Ar*)(Cp*)Th(PhCH-CC-CHPh)] (4).
Published: 2019
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28. Electronic and spin delocalization in a switchable trinuclear triphenylene trisemiquinone bridged Ni3 complex

Author: François Lambert, Talal Mallah, Eric Rivière, Yiting Wang, Régis Guillot, Christian Herrero, Zakaria Halime, Antoine Tissot, Université Grenoble Alpes - UFR Langage, lettres et arts du spectacle, information et communication - Dpt Sciences de l'information et de la communication (UGA UFR LLASIC SIC), Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), Institut de Neurosciences cognitives et intégratives d'Aquitaine (INCIA), Université Bordeaux Segalen - Bordeaux 2-Université Sciences et Technologies - Bordeaux 1-SFR Bordeaux Neurosciences-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie Moléculaire et des Matériaux d'Orsay (ICMMO), Université Paris-Sud - Paris 11 (UP11)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Institut des Matériaux Poreux de Paris (IMAP ), Département de Chimie - ENS Paris, École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-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)-Centre National de la Recherche Scientifique (CNRS), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), and Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Materials science, Triphenylene, 010402 general chemistry, 01 natural sciences, Catalysis, law.invention, Paramagnetism, chemistry.chemical_compound, Delocalized electron, Deprotonation, law, Materials Chemistry, [CHIM]Chemical Sciences, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Electron paramagnetic resonance, Spin (physics), Open shell, ComputingMilieux_MISCELLANEOUS, 010405 organic chemistry, Metals and Alloys, Bridging ligand, General Chemistry, 0104 chemical sciences, 3. Good health, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Crystallography, chemistry, Ceramics and Composites
Abstract: A trinuclear triphenylene trisemiquinone complex containing paramagnetic NiII is obtained under ambient conditions from the reaction of deprotonated tricatecholate hexahydroxytriphenylene (H6HHTP) with NiII capped with a trispyrazolyl borate tridentate ligand. The magnetic and EPR data are consistent with delocalization of the electronic spin over the three NiII species. The two-electron reduced complex shows an EPR spectrum corresponding to a S = 1/2 species due to a large antiferromagnetic coupling between the radical and only one of the NiII ions highlighting the localization of the electronic spin. No EPR signal is observed for the one- and three-electron reduced species consistent with the closed shell of the bridging ligand.
Published: 2019
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29. High-valence CuIICuIII species in action: demonstration of aliphatic C–H bond activation at room temperature

Author: Christian Philouze, Amélie Durand, Aurore Thibon-Pourret, Nicolas Le Poul, Catherine Belle, James A. Isaac, Département de Chimie Moléculaire (DCM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), Département de Chimie Moléculaire - Chimie Inorganique Redox Biomimétique (DCM - CIRE ), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), Institut de Chimie Moléculaire de Grenoble (ICMG), Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), Chimie, Electrochimie Moléculaires et Chimie Analytique (CEMCA), Université de Brest (UBO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO), Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA), Université Joseph Fourier - Grenoble 1 (UJF)-Centre National de la Recherche Scientifique (CNRS), Institut Brestois Santé Agro Matière (IBSAM), and Université de Brest (UBO)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)
Subjects: aliphatic C–H bond activation, Reactive intermediate, chemistry.chemical_element, CuII, Oxidative phosphorylation, 010402 general chemistry, Photochemistry, 01 natural sciences, Catalysis, chemistry.chemical_compound, Materials Chemistry, [CHIM]Chemical Sciences, CuIICuIII, C h bond, Valence (chemistry), 010405 organic chemistry, Chemistry, Metals and Alloys, [CHIM.CATA]Chemical Sciences/Catalysis, General Chemistry, Copper, Toluene, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, C-H bond activation, copper, Ceramics and Composites, CuIII, Stoichiometry
Abstract: International audience; The electrochemically generated CuIICuIII mixed-valence species promotes activation of strong aliphatic C–H bonds (i.e. toluene) at room temperature. The mechanistic pathway turns from stoichiometric to catalytic upon addition of base, hence demonstrating that such high-valence dicopper species can be key reactive intermediates in copper-based oxidative processes.
Published: 2019
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30. Reduction of 1,3,5,7-cyclooctatetraene by a molecular calcium hydride: an even electron polarised insertion/deprotonation mechanism

Author: Mary F. Mahon, Emma Richards, Chiara Dinoi, Laurent Maron, Andrew S. S. Wilson, Michael S. Hill, Department of Chemistry [Bath], University of Bath [Bath], 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)-Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), School of Chemistry [Cardiff], Cardiff University, and EPSRC [EP/N014456/1, EP/R020752/1] Funding Source: UKRI
Subjects: Calcium hydride, 010405 organic chemistry, Hydride, Metals and Alloys, General Chemistry, Annulene, 010402 general chemistry, Photochemistry, 01 natural sciences, Catalysis, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, chemistry.chemical_compound, Cyclooctatetraene, Deprotonation, chemistry, Reagent, Materials Chemistry, Ceramics and Composites, Reactivity (chemistry), [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], Derivative (chemistry)
Abstract: Reaction of a dimeric β-diketiminato calcium hydride with 1,3,5,7-cyclooctatetraene enables two electron aromatisation of the [8]annulene to provide an inverse sandwich dicalcium cyclooctatetraenyl derivative. This reactivity does not proceed through sequential single electron transfer but via a consecutive polarised Ca-H/C[double bond, length as m-dash]C insertion and deprotonation pathway that occurs at the intact dimeric hydride reagent.
Published: 2019
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31. Improved single-chain-magnet behavior in a biradical-based nitronyl nitroxide-Cu–Dy chain

Author: Juan Sun, Hongdao Li, Licun Li, Jean-Pascal Sutter, Meng Yang, Jing Xie, Key Laboratory of Advanced Energy Materials Chemistry, Nankai University, Nankai University (NKU), Laboratoire de chimie de coordination (LCC), 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)-Centre National de la Recherche Scientifique (CNRS), 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: Nitroxide mediated radical polymerization, Materials science, 010405 organic chemistry, Magnetization reversal, Metals and Alloys, General Chemistry, Single chain, 010402 general chemistry, 01 natural sciences, Catalysis, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Crystallography, Chain (algebraic topology), Ferromagnetism, Intramolecular force, Magnet, Materials Chemistry, Ceramics and Composites, [CHIM.COOR]Chemical Sciences/Coordination chemistry
Abstract: International audience; A biradical with ferromagnetic intramolecular interaction was found to improve the SCM behavior of a nitronyl nitroxide-Cu–Dy chain, resulting in an energy barrier for magnetization reversal of 40 K.
Published: 2019
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32. A versatile and recyclable molecularly imprinted polymer as an oxidative catalyst of sulfur derivatives: a new possible method for mustard gas and V nerve agent decontamination

Author: Julie Hardouin, Rachid Baati, François Estour, Emilie Petit, Sébastien Balieu, Damien Schapman, Sophie Mohamed, Ludovic Galas, 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), Plate-Forme de Recherche en Imagerie Cellulaire de Haute-Normandie (PRIMACEN), Normandie Université (NU)-Normandie Université (NU)-Institute for Research and Innovation in Biomedicine (IRIB), Normandie Université (NU)-Normandie Université (NU)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Polymères Biopolymères Surfaces (PBS), 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)-Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS), Institut de chimie et procédés pour l'énergie, l'environnement et la santé (ICPEES), Université de Strasbourg (UNISTRA)-Matériaux et nanosciences d'Alsace (FMNGE), and Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)
Subjects: chemistry.chemical_element, 010402 general chemistry, Heterogeneous catalysis, 01 natural sciences, Catalysis, chemistry.chemical_compound, Materials Chemistry, medicine, [CHIM]Chemical Sciences, Catalytic efficiency, Nerve agent, 010405 organic chemistry, Chemistry, Metals and Alloys, Molecularly imprinted polymer, General Chemistry, Human decontamination, Combinatorial chemistry, Porphyrin, Sulfur, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Ceramics and Composites, medicine.drug
Abstract: International audience; A molecularly imprinted polymer containing a porphyrin unit was developed as a biomimetic heterogenous catalyst for the oxidation of sulfur derivatives. Its catalytic efficiency under mild conditions and its easy recovery represent a great asset for the design of new decontamination tools for yperite and VX.
Published: 2019
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33. Aluminum substitution for vanadium in the Na3V2(PO4)2F3 and Na3V2(PO4)2FO2 type materials

Author: Dany Carlier, Laurence Croguennec, Thibault Broux, François Fauth, Jacob Olchowka, Christian Masquelier, Paula Sanz Camacho, Emmanuel Petit, Long H. B. Nguyen, Institut de Chimie de la Matière Condensée de Bordeaux (ICMCB), Université de Bordeaux (UB)-Institut Polytechnique de Bordeaux-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Réseau sur le stockage électrochimique de l'énergie (RS2E), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Aix Marseille Université (AMU)-Université de Pau et des Pays de l'Adour (UPPA)-Université de Nantes (UN)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Advanced Lithium Energy Storage Systems - ALISTORE-ERI (ALISTORE-ERI), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire réactivité et chimie des solides - UMR CNRS 7314 (LRCS), Université de Picardie Jules Verne (UPJV)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), ALBA Synchrotron light source [Barcelone], The authors thank the RS2E and Alistore-ERI Networks for the funding, as well as the financial support of Région Nouvelle Aquitaine, of the French National Research Agency (STORE-EX Labex Project ANR-10-LABX-76-01 and SODIUM Descartes project ANR-13-DESC-0001-02) and of the H2020 research and innovation program under the Grant Agreement No. 646433-NAIADES. The authors also want to thank C. DENAGE, A. FARGUES and E. LEBRAUD (ICMCB) for their help., ANR-10-LABX-0076,STORE-EX,Laboratory of excellency for electrochemical energy storage(2010), ANR-13-DESC-0001,SODIUM,Batteries à ions sodium pour des robots télécommandés(2013), European Project: 646433,H2020,H2020-LCE-2014-3,NAIADES(2015), Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA), and Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Materials science, Inorganic chemistry, Vanadium, chemistry.chemical_element, 02 engineering and technology, 010402 general chemistry, Electrochemistry, 01 natural sciences, Catalysis, Aluminium, Oxidation state, Materials Chemistry, Electrode material, Final product, Substitution (logic), Metals and Alloys, [CHIM.MATE]Chemical Sciences/Material chemistry, General Chemistry, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, chemistry, Ceramics and Composites, 0210 nano-technology, Solid solution
Abstract: International audience; Among the positive electrode materials for Na-ion batteries, Na3V2(PO4)2F3 is considered as one of the most promising and generates high interest. Here, we study the influence of the sol–gel synthesis parameters on the structure and on the electrochemical signature of the partially substituted Na3V2−zAlz(PO4)2(F,O)3 materials. We demonstrate that the acidity of the starting solution influences the vanadium oxidation state of the final product. For the first time we report on the possibility of controlling the double Al/V and O/F substitution that leads to the preparation of the Na3V2−zAlz(PO4)2F1+zO2−z solid solution.
Published: 2019
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34. Activation of olefin metathesis complexes containing unsymmetrical unsaturated N-heterocyclic carbenes by copper and gold transmetalation

Author: Jean-Paul Guégan, Olivier Baslé, Sophie Colombel-Rouen, Mathieu Rouen, Vincent Dorcet, Fadwa Kamal, Thierry Roisnel, Marc Mauduit, Adrien Dumas, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), DEMETA SAS, 2014/0702, Association Nationale de la Recherche et de la Technologie. We thank the Centre National de la Recherche Scientifique (CNRS) and the Ecole Nationale Supérieure de Chimie de Rennes (ENSCR). This work was supported by the ANRT and DEMETA S.A.S. (CIFRE no. 2014/0702 and 2017/0873, grants to A. D. and F. K.). We are grateful to Elsa Caytan and the PRISM core facility (Biogenouest©, UMS, Biosit, Université de Rennes 1) for NRM experiences., Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Olefin metathesis, 010405 organic chemistry, Ligand, Chemistry, Metals and Alloys, chemistry.chemical_element, General Chemistry, 010402 general chemistry, Metathesis, 01 natural sciences, Copper, Catalysis, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Transmetalation, Polymer chemistry, Materials Chemistry, Ceramics and Composites, [CHIM]Chemical Sciences
Abstract: International audience; The activation of ruthenium-indenylidene complexes containing two unsymmetrical unsaturated N-heterocyclic carbenes (u2-NHCs) by a transmetalation process is reported. The use of copper(i) or gold(i) chlorides promotes the rapid trapping of one NHC ligand, which releases the catalytically active Ru-species. Impressive initiation rates with full-conversions are observed within one minute. This practical protocol demonstrates excellent catalytic performances in various ring-closing metathesis (RCM) and self-metathesis (SM) reactions.
Published: 2019
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35. Carbonylation of tertiary carbon radicals: synthesis of lactams

Author: Zhuan Zhang, Xiao-Feng Wu, Youcan Zhang, Zhiping Yin, Pierre H. Dixneuf, Universität Rostock, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)
Subjects: 010405 organic chemistry, Chemistry, Radical, Metals and Alloys, Atom (order theory), chemistry.chemical_element, General Chemistry, 010402 general chemistry, Photochemistry, 01 natural sciences, Catalysis, 0104 chemical sciences, 3. Good health, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Materials Chemistry, Ceramics and Composites, [CHIM]Chemical Sciences, Carbonylation, Carbon, ComputingMilieux_MISCELLANEOUS
Abstract: Herein, we disclose an interesting iron-catalyzed approach for the carbonylation of a tertiary carbon radical. The tertiary carbon radical generated from a 1,5-hydrogen atom transfer can be captured by CO gas smoothly. Various six-membered lactams were constructed chemo-selectively in high yields.
Published: 2019
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36. Probing the in-air growth of large area of 3D functional structures into a 2D supramolecular nanoporous network

Author: Lydia Sosa-Vargas, Lydia Hamitouche, Céline Paris, Romain Brisse, André Jean Attias, Christophe Petit, Imad Arfaoui, Vincent Humblot, Christelle Mansuy, Vanessa Labet, Dominique Guianvarc'h, Sandrine Sagan, David Kreher, 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 des biomolécules (LBM UMR 7203), Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Département de Chimie - ENS Paris, École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Chimie Moléculaire de Paris Centre (FR 2769), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-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 Pierre et Marie Curie - Paris 6 (UPMC)-Institut National de la Santé et de la Recherche Médicale (INSERM), 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), Laboratoire de Réactivité de Surface (LRS), and Yonsei University
Subjects: Materials science, Resonance Raman spectroscopy, Supramolecular chemistry, chemistry.chemical_element, Nanotechnology, 02 engineering and technology, Substrate (electronics), 010402 general chemistry, 01 natural sciences, Catalysis, Contact angle, Materials Chemistry, [CHIM]Chemical Sciences, Porosity, Nanoporous, Metals and Alloys, General Chemistry, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, chemistry, Ceramics and Composites, Surface modification, 0210 nano-technology, Carbon
Abstract: International audience; Surface-confined host–guest chemistry at the air/solid interface is used for trapping a functionalized 3D Zn–phthalocyanine complex into a 2D porous supramolecular template allowing the large area functionalization of an sp2-hybridized carbon-based substrate as evidenced by STM, resonance Raman spectroscopy, and water contact angle measurements.
Published: 2018
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37. The Ouzo effect to selectively assemble molybdenum clusters into nanomarbles or nanocapsules with increased HER activity

Author: Pierric Lemoine, Yann Molard, Corinne Lagrost, Alain Moréac, Jérôme Cuny, Soizic Chevance, Fabienne Gauffre, Stéphane Cordier, Flavien Sciortino, Toshiaki Takei, Fabien Grasset, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Modélisation, Agrégats, Dynamique (LCPQ) (MAD), Laboratoire de Chimie et Physique Quantiques (LCPQ), Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), 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 du CNRS (INC)-Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Laboratory for Innovative Key Materials and Structures (LINK), SAINT-GOBAIN-National Institute of Materials Science-Centre National de la Recherche Scientifique (CNRS), Institut de Physique de Rennes (IPR), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Centre National de la Recherche Scientifique (CNRS), International Center for Materials Nanoarchitectonics (MANA), National Institute for Materials Science (NIMS), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Université de Toulouse (UT)-Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Saint-Gobain-National Institute of Materials Science-Centre National de la Recherche Scientifique (CNRS), Université de Rennes (UR)-Centre National de la Recherche Scientifique (CNRS), and Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3)
Subjects: Materials science, Cluster chemistry, Nanoparticle, 02 engineering and technology, 010402 general chemistry, Electrochemistry, 01 natural sciences, Catalysis, Nanocapsules, Metal, Ouzo effect, Materials Chemistry, Cluster (physics), Metals and Alloys, [CHIM.MATE]Chemical Sciences/Material chemistry, General Chemistry, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Chemical engineering, visual_art, Ceramics and Composites, visual_art.visual_art_medium, Water splitting, 0210 nano-technology
Abstract: International audience; Metal cluster nanoparticles are obtained by simple solvent shifting called the Ouzo effect. Remarkably, the assembly of [{Mo6Br8}L6]2− (L = Br− or NCS−) cluster units can be directed into nanomarbles or nanocapsules depending on the cluster chemistry. When deposited on electrodes, these nanoparticles show good activities in electrochemical water splitting under mild conditions.
Published: 2018
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38. O–O bond cleavage via electrochemical reduction of a side-on peroxo dicopper model of hemocyanin

Author: Masahito Kodera, Ana Gabriela Porras-Gutierrez, Isidoro López, Bénédicte Douziech, Laurianne Wojcik, N Le Poul, Y. Le Mest, Chimie, Electrochimie Moléculaires et Chimie Analytique (CEMCA), Université de Brest (UBO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Brestois Santé Agro Matière (IBSAM), Université de Brest (UBO), 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), Department of moleclar science and technology - Doshisha University - Kyotanabe - Japan, and Doshisha University [Kyoto]
Subjects: medicine.medical_treatment, Electrons, 010402 general chemistry, Cleavage (embryo), Electrochemistry, 01 natural sciences, Redox, Catalysis, Biomimetic Materials, Coordination Complexes, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Polymer chemistry, Materials Chemistry, medicine, [CHIM]Chemical Sciences, Molecule, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Bond cleavage, Peroxo complex, Molecular Structure, 010405 organic chemistry, Chemistry, Ligand, Metals and Alloys, Hemocyanin, Bioinorganic chemistry, Electrochemical Techniques, General Chemistry, O-O bond cleavage, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Oxygen, electrochemistry, copper, Hemocyanins, Ceramics and Composites, Thermodynamics, [CHIM.OTHE]Chemical Sciences/Other, Oxidation-Reduction
Abstract: International audience; The redox properties of the μ-η2:η2 peroxo complex [Cu2(H6M4h)(O2)]2+ were elucidated. This study constitutes the first full electrochemical and spectroelectrochemical characterization of a side-on peroxo Cu2:O2 bioinorganic model complex. The peroxo complex is irreversibly reduced in a two- electron process localized on the peroxo ligand triggering the cleavage of the O-O bond; Les propriétés redox du complexe peroxo μ-η2:η2 [Cu2(H6M4h)(O2)]2+, modèle de l’hémocyanine, ont été élucidées par des études électrochimiques et spectroélectrochimiques. La réduction du complexe peroxo est irréversible et s’effectue selon un processus à deux électrons localisé sur le ligand peroxyde, déclenchant la rupture de la liaison O-O.
Published: 2018
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39. Diazachlorin and diazabacteriochlorin for one- and two-photon photodynamic therapy

Author: Morgane Daurat, Jean-François Longevial, Tsubasa Nishimura, Dongho Kim, Juwon Oh, Sébastien Richeter, Wen Xi Chia, Ayaka Yamaji, Yoshihiro Miyake, Magali Gary-Bobo, Christophe Nguyen, Gakhyun Kim, Dina Aggad, Hiroshi Shinokubo, Sébastien Clément, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Institut des Biomolécules Max Mousseron [Pôle Chimie Balard] (IBMM), 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), and Soongsil University
Subjects: Models, Molecular, medicine.medical_treatment, education, Breast Neoplasms, Photodynamic therapy, [CHIM.THER]Chemical Sciences/Medicinal Chemistry, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Catalysis, Two-photon excitation microscopy, In vivo, Cell Line, Tumor, Materials Chemistry, medicine, Animals, Humans, Zebrafish, health care economics and organizations, Photons, Photosensitizing Agents, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Chemistry, Metals and Alloys, General Chemistry, 021001 nanoscience & nanotechnology, In vitro, 3. Good health, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Photochemotherapy, MCF-7 Cells, Ceramics and Composites, Cancer research, Female, 0210 nano-technology
Abstract: International audience; Diazachlorin and diazabacteriochlorin have been prepared through reduction of diazaporphyrin and their in vitro and in vivo activity in photodynamic therapy has been investigated.
Published: 2018
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40. Kinetic stabilisation of a molecular strontium hydride complex using an extremely bulky amidinate ligand

Author: Thomas Sutcliffe, Laurent Maron, Caspar N. de Bruin-Dickason, Cameron Jones, Glen B. Deacon, Carlos Alvarez Lamsfus, School of Chemistry, Monash University, 3800 Clayton, Victoria (Australie), Monash University [Clayton], 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)-Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Australian Research Council, U.S. Air Force Asian Office of Aerospace Research and Development [FA2386-18-1-0125], and Alexander von Humboldt Foundation
Subjects: Strontium, Alkaline earth metal, 010405 organic chemistry, Ligand, Chemistry, Hydride, Magnesium hydride, Metals and Alloys, chemistry.chemical_element, General Chemistry, 010402 general chemistry, Kinetic energy, 01 natural sciences, Catalysis, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Crystallography, chemistry.chemical_compound, Materials Chemistry, Ceramics and Composites, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph]
Abstract: International audience; Two extremely bulky amidinate ligands, [RC{N(Dip)}{N(Ar-dagger)}](-) (Dip = 2,6-diisopropylphenyl; Ar-dagger = C6H2{C(H)Ph-2}(2)Pr-i-2,6,4; R = 1-adamantyl (L-Ad), tert-butyl (L-tBu)) have been developed and utilised for the kinetic stabilisation of the strontium and magnesium hydride complexes, [(LSr)-Sr-Ad(mu-H)](2) and [(LMg)-Mg-R(mu-H)](2) (R = Ad or Bu-t). The former represents the missing link in the series of dimeric systems, [LAe(mu-H)](2) (Ae = alkaline earth metal). The structure and bonding of the complexes have been studied by crystallographic, spectroscopic and computational techniques.
Published: 2018
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41. Synthesis and structural characterization of the first neptunium based metal–organic frameworks incorporating {Np6O8} hexanuclear clusters

Author: Pascal Roussel, Sylvain Duval, Juliane März, Hervé Feuchter, Natacha Henry, Thierry Loiseau, Atsushi Ikeda-Ohno, Christophe Volkringer, Nicolas P. Martin, Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Helmholtz-Zentrum Dresden-Rossendorf (HZDR), Institut Universitaire de France (IUF), Ministère de l'Education nationale, de l’Enseignement supérieur et de la Recherche (M.E.N.E.S.R.), and Centrale Lille Institut (CLIL)-Université d'Artois (UA)-Centrale Lille-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Lille
Subjects: 010405 organic chemistry, Chemistry, Neptunium, Metals and Alloys, chemistry.chemical_element, General Chemistry, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 01 natural sciences, Combinatorial chemistry, Catalysis, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Characterization (materials science), Hydrolysis, Materials Chemistry, Ceramics and Composites, Metal-organic framework, ComputingMilieux_MISCELLANEOUS, Transuranium element
Abstract: Successful synthesis of the first transuranium metal-organic frameworks (TRU-MOFs) involving tetravalent Np4+ is reported. These compounds were obtained from the controlled hydrolysis of Np4+ in the presence of dicarboxylate ligands. The final structures contain the [Np6O4(OH)4(H2O)6]12+ unit, which were never crystallized before with tetravalent neptunium, associated with ditopic ligands.
Published: 2018
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42. 3D supramolecular self-assembly of [60]fullerene hexaadducts decorated with triarylamine molecules

Author: Nicolas Giuseppone, Eric Buhler, Mounir Maaloum, Jean-François Nierengarten, Thi Minh Nguyet Trinh, Emilie Moulin, Odile Gavat, Thomas Ellis, Guillaume Fleith, Laboratoire de chimie moléculaire (LCM), Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Substances naturelles/chimie moléculaire, Université Louis Pasteur - Strasbourg I-Ecole européenne de chimie, polymères et matériaux [Strasbourg]-Centre National de la Recherche Scientifique (CNRS), Institut Charles Sadron (ICS), Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Animal et gestion intégrée des risques (UPR AGIRs), Centre de Coopération Internationale en Recherche Agronomique pour le Développement (Cirad), Laboratoire d'innovation moléculaire et applications (LIMA), and Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Fullerene, Materials science, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Metals and Alloys, Supramolecular chemistry, Nanowire, General Chemistry, 010402 general chemistry, Grafting, 01 natural sciences, Catalysis, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, chemistry.chemical_compound, Monomer, chemistry, Polymerization, Polymer chemistry, Materials Chemistry, Ceramics and Composites, Molecule, Self-assembly
Abstract: A clickable fullerene hexa-adduct scaffold has been functionalized with twelve triarylamine subunits. The light-triggered self-assembly of this molecular unit leads to 3D honeycomb-like structures with inner pores of around 10 nm diameter. Multiple grafting of triarylamine subunits onto a hard-core C60 unit increases the dimensionality of the self-assembly process by reticulating the 1D nanowires typically obtained from the supramolecular polymerization of triarylamine monomers.
Published: 2018
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43. Alpha-helical folding of SilE models upon Ag(His)(Met) motif formation

Author: Olivier Walker, Olivier Sénèque, Katharina M. Fromm, Valentin Chabert, Maggy Hologne, Dept Chem, University of Fribourg, Biophysics of complex systems, Institut des Sciences Analytiques (ISA), Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS), 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 [2016-2019] (UGA [2016-2019]), Université de Fribourg = University of Fribourg (UNIFR), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut 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)
Subjects: 0301 basic medicine, Chemistry, Stereochemistry, Metals and Alloys, General Chemistry, Catalysis, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, 03 medical and health sciences, Resistant bacteria, 030104 developmental biology, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Materials Chemistry, Ceramics and Composites, [CHIM]Chemical Sciences
Abstract: International audience; The SilE protein is suspected to have a prominent role in Ag + detoxification of silver resistant bacteria. Using model peptides, we elucidated both qualitative and quantitative aspects of the Ag +-induced α-helical structuring role of His-and Met-rich sequences of SilE, improving our understanding of its function within the Sil system.
Published: 2018
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44. Electron transfer in a covalent dye–cobalt catalyst assembly – a transient absorption spectroelectrochemistry perspective

Author: Ying Zhang, Benjamin Dietzek, Vincent Artero, Linda Zedler, Sebastian Bold, Julien Massin, Murielle Chavarot-Kerlidou, Institute of Physical Chemistry and Abbe Center of Photonics, Friedrich-Schiller-Universität = Friedrich Schiller University Jena [Jena, Germany], Leibniz Institute of Photonic Technology Jena, Department Functional Interfaces, Albert-Einstein-Straße 9, 07745 Jena, Germany, Laboratoire de Chimie et Biologie des Métaux (LCBM - UMR 5249), 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), 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), Institute for Physical Chemistry and Center for Energy and Environmental Chemistry, Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-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)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])
Subjects: inorganic chemicals, Quenching (fluorescence), 010405 organic chemistry, Chemistry, Metals and Alloys, chemistry.chemical_element, [CHIM.CATA]Chemical Sciences/Catalysis, General Chemistry, 010402 general chemistry, Photochemistry, 01 natural sciences, Catalysis, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Cobalt catalyst, Electron transfer, Oxidation state, Covalent bond, Ultrafast laser spectroscopy, Materials Chemistry, Ceramics and Composites, [CHIM]Chemical Sciences, Cobalt
Abstract: International audience; Various oxidation states of the catalytically active cobalt center in a covalent dyad were electrochemically prepared and the light-induced excited-state processes were studied. Virtually identical deactivation processes are observed, irrespective of the oxidation state of the cobalt center, varying from CoIII to CoI, indicating the absence of oxidative quenching within the dye-catalyst assembly.
Published: 2018
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45. Cofacial porphyrin dimers assembled from N-heterocyclic carbene–metal bonds

Author: Clémence Rose, Sébastien Clément, Aurélien Lebrun, Sébastien Richeter, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Institut des Biomolécules Max Mousseron [Pôle Chimie Balard] (IBMM), and 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)
Subjects: 010405 organic chemistry, Metals and Alloys, General Chemistry, 010402 general chemistry, 01 natural sciences, Porphyrin, Catalysis, 0104 chemical sciences, 3. Good health, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, chemistry.chemical_compound, chemistry, Polymer chemistry, Materials Chemistry, Ceramics and Composites, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Carbene, ComputingMilieux_MISCELLANEOUS, Metallic bonding
Abstract: A porphyrin bearing four imidazolium rings on the meso positions was used as an N-heterocyclic carbene (NHC) precursor for the synthesis of porphyrin dimers with face-to-face orientations. The porphyrins are connected through the formation of eight M-CNHC bonds, with M = AgI or AuI.
Published: 2018
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46. Manganese catalyzed reductive amination of aldehydes using hydrogen as a reductant

Author: Dmitry A. Valyaev, Jean-Baptiste Sortais, Duo Wei, Noël Lugan, Antoine Bruneau-Voisine, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de chimie de coordination (LCC), 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)-Centre National de la Recherche Scientifique (CNRS), Institut Universitaire de France (IUF), Ministère de l'Education nationale, de l’Enseignement supérieur et de la Recherche (M.E.N.E.S.R.), Centre National de la Recherche Scientifique, Institut Universitaire de France, ANR-15-CE07-0001, Agence Nationale de la Recherche, ANR-15-CE07-0001,Ferracycles,Synthèse et application en catalyse de complexes cyclométalés du fer obtenus par activation C-H(2015), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), 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: Hydrogen, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Condensation, Metals and Alloys, chemistry.chemical_element, General Chemistry, Manganese, Alkylation, 010402 general chemistry, 01 natural sciences, Reductive amination, Catalysis, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, chemistry, Polymer chemistry, Materials Chemistry, Ceramics and Composites, [CHIM]Chemical Sciences
Abstract: International audience; A one-pot two-step procedure was developed for the alkylation of amines via reductive amination of aldehydes using molecular dihydrogen as a reductant in the presence of a manganese pyridinyl-phosphine complex as a pre-catalyst. After the initial condensation step, the reduction of imines formed in situ is performed under mild conditions (50-100 degrees C) with 2 mol% of catalyst and 5 mol% of tBuOK under 50 bar of hydrogen. Excellent yields (>90%) were obtained for a large combination of aldehydes and amines (40 examples), including aliphatic aldehydes and amino-alcohols.
Published: 2018
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47. {Np38} clusters: the missing link in the largest poly-oxo cluster series of tetravalent actinides

Author: Juliane März, Christophe Volkringer, Christoph Hennig, Nicolas P. Martin, Thierry Loiseau, Pascal Roussel, Atsushi Ikeda-Ohno, Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Institut Universitaire de France (IUF), Ministère de l'Education nationale, de l’Enseignement supérieur et de la Recherche (M.E.N.E.S.R.), Institute of Resource Ecology [Dresden] (IRE), Helmholtz-Zentrum Dresden-Rossendorf (HZDR), and Centrale Lille Institut (CLIL)-Université d'Artois (UA)-Centrale Lille-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Lille
Subjects: Series (mathematics), 010405 organic chemistry, Neptunium, Solvothermal synthesis, Metals and Alloys, chemistry.chemical_element, General Chemistry, Link (geometry), Actinide, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 01 natural sciences, Catalysis, 0104 chemical sciences, 3. Good health, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, chemistry.chemical_compound, Crystallography, chemistry, Materials Chemistry, Ceramics and Composites, Cluster (physics), ComputingMilieux_MISCELLANEOUS, Tetrahydrofuran
Abstract: Two poly-oxo cluster complexes of tetravalent neptunium (Np(iv)), Np38O56Cl18(bz)24(THF)8·nTHF and Np38O56Cl42(ipa)20·mipa (bz = benzoate, THF = tetrahydrofuran, and ipa = isopropanol), were obtained via solvothermal synthesis and structurally characterised by single-crystal X-ray diffraction. The {Np38} clusters are comparable to the analogous {U38} and {Pu38} motifs, filling the gap in this largest poly-oxo cluster series of tetravalent actinides.
Published: 2018
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48. Electronic effects of the Bernal stacking of graphite on self-assembled aromatic adsorbates

Author: Nataliya Kalashnyk, André Jean Attias, Maud Jaouen, Ludovic Douillard, Céline Fiorini-Debuisschert, Fabrice Charra, Laboratoire d'Electronique et nanoPhotonique Organique (LEPO), 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 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), Yonsei University Seoul, Korea, 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, Stacking, 02 engineering and technology, Substrate (electronics), 010402 general chemistry, 01 natural sciences, Catalysis, law.invention, Adsorption, law, Monolayer, Materials Chemistry, Honeycomb, Graphite, [PHYS]Physics [physics], Graphene, Metals and Alloys, General Chemistry, 021001 nanoscience & nanotechnology, 3. Good health, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Crystallography, Ceramics and Composites, Scanning tunneling microscope, 0210 nano-technology
Abstract: International audience; We compare by Scanning Tunneling Microscopy (STM) self-organized honeycomb monolayers of aromatic molecules formed either on graphite or on graphene. A differential contrast between the adsorption sites observed exclusively on graphite evidences the electronic effects of the symmetry breaking by the staggered atomic layers forming this substrate.
Published: 2018
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49. Computational structure determination of novel metal–organic frameworks

Author: Guillaume Maurin, Benjamin J. Sikora, Mohammad Wahiduzzaman, Christian Serre, Sujing Wang, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Institut des Matériaux Poreux de Paris (IMAP ), Département de Chimie - ENS Paris, École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), and Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Materials science, Tandem, 010405 organic chemistry, Metals and Alloys, Structure (category theory), Nanotechnology, [CHIM.MATE]Chemical Sciences/Material chemistry, General Chemistry, 010402 general chemistry, 01 natural sciences, Catalysis, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Materials Chemistry, Ceramics and Composites, [CHIM]Chemical Sciences, Metal-organic framework
Abstract: International audience; A structure prediction tool has been developed to guide the discovery of MOF materials. This computational strategy has been trained over a series of existing MOFs and further successfully applied in tandem with an experimental effort to produce novel Zr MOFs based on naturally occurring carboxylic acids.
Published: 2018
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50. Well-defined palladium–ceria interfacial electronic effects trigger CO oxidation

Author: Christian George, Junxiao Chen, Xingfu Tang, Mimoun Aouine, Weiye Qu, Philippe Vernoux, Yaxin Chen, IRCELYON-Catalytic and Atmospheric Reactivity for the Environment (CARE), Institut de recherches sur la catalyse et l'environnement de Lyon (IRCELYON), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université 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 IRCELYON-Microscopie (MICROSCOPIE)
Subjects: Inert, Materials science, 010405 organic chemistry, Metals and Alloys, chemistry.chemical_element, [CHIM.CATA]Chemical Sciences/Catalysis, General Chemistry, 010402 general chemistry, [SDE.ES]Environmental Sciences/Environmental and Society, 01 natural sciences, 7. Clean energy, Catalysis, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Electron transfer, chemistry, Chemical engineering, Materials Chemistry, Ceramics and Composites, Electronic effect, Nanorod, Well-defined, Palladium
Abstract: Metal-support electronic interactions were investigated in CO oxidation by using a Pd/CeO2 model catalyst with well-defined interfaces, and electron transfer from Pd cubes to CeO2 nanorods through interfaces triggered CO oxidation at low temperature where standalone Pd and CeO2 are inert.
Published: 2018
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