Author: "Institut de Chimie du CNRS (INC)" / Topic: 010402 general chemistry - Searchworks@Jio Institute Digital Library Search Results

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50,344 results on '"Institut de Chimie du CNRS (INC)"'

1. CuO-CeO2 catalysts based on SBA-15 and SBA-16 for COPrOx. Influence of oxides concentration, incorporation method and support structure

Author: Albano M. Lacoste, Magali Bonne, Inés S. Tiscornia, Bénédicte Lebeau, Alicia Viviana Boix, Instituto de Investigaciones en Catálisis y Petroquímica 'Ing. José Miguel Parera' [Santa Fe] (INCAPE), Consejo Nacional de Investigaciones Científicas y Técnicas [Buenos Aires] (CONICET)-Universidad Nacional del Litoral [Santa Fe] (UNL), Institut de Science des Matériaux de Mulhouse (IS2M), Centre National de la Recherche Scientifique (CNRS)-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-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))-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)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), and univOAK, Archive ouverte
Subjects: [CHIM.MATE] Chemical Sciences/Material chemistry, Materials science, 010405 organic chemistry, impregnation methods, active phase concentration, [CHIM.CATA] Chemical Sciences/Catalysis, Nanoparticle, [CHIM.MATE]Chemical Sciences/Material chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, General Chemistry, COPrOx, Mesoporous silica, porous mesostructure, 010402 general chemistry, 01 natural sciences, Redox, Catalysis, 0104 chemical sciences, Adsorption, X-ray photoelectron spectroscopy, Chemical engineering, SBA-15/SBA-16, Mesoporous material, Incipient wetness impregnation
Abstract: In this work different variables that can affect the catalytic behavior of CuO-CeO2 supported on mesoporous silica (SBA-15 and SBA-16) were studied. The influence on the COPrOx activity of the relative concentration of the CuO and CeO2 active phase and different impregnation methods in mesoporous support was analyzed. The physicochemical characterization was performed EDS-SEM and TEM-STEM, N2 isotherms, X-ray Diffraction (XRD) and X-ray Photoelectron Spectroscopy (XPS). The incipient wetness impregnation method (IWI) was the better alternative to introduce the active phases compared to solid state impregnation (SSI). In addition, the catalysts based on 2-D structure of SBA-15 were more active and selective than those based in 3-D SBA-16. In general, the high surface area of the supports benefited the dispersion of CuO and CeO2 oxides nanoparticles. All catalysts displayed the preservation of the mesostructure and the formation of nanoparticles of active phases (less than 10 nm) detected by TEM. The best COPrOx catalyst, obtained from the SBA-15 fibers by IWI method, with a relative CuO concentration of 0.2, exhibited XCO ≥ 99% at 175 °C and above 90% in a wide window of temperatures. This catalyst showed an adequate performance in presence of CO2 and H2O and good recovery of CO conversion and selectivity. The analysis by XPS revealed that the majority species were Ce4+, however in some catalysts Ce3+ species are also present, which are associated with vacancies oxygen and favor the redox process. In addition, Cu2+ and Cu+ species are present, the latter recognized as a key site of CO adsorption in the reaction mechanism.
Published: 2022
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2. Structurally characterised new twisted conformer for cyclen, controlled by metal ion complexation as seen in NiII and CuII complexes with halides and pseudohalides

Author: Jean-Pascal Sutter, Sakharam B. Tayade, Nattamai Bhuvanesh, Avinash S. Kumbhar, Abhineet Verma, Kateryna Bretosh, Joseph H. Reibenspies, Sailaja S. Sunkari, Department of Chemistry, Banaras Hindu University, Banaras Hindu University [Varanasi] (BHU), Texas A&M University [Galveston], Savitribai Phule Pune University [India], Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), DST, New Delhi, India (Project code : DST/YSS/2015/000993), Institut de Chimie de Toulouse (ICT), 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, 010405 organic chemistry, Chemistry, Metal ions in aqueous solution, General Chemistry, Dihedral angle, 010402 general chemistry, Condensed Matter Physics, 01 natural sciences, 0104 chemical sciences, Metal, chemistry.chemical_compound, Crystallography, Cyclen, visual_art, visual_art.visual_art_medium, Antiferromagnetism, Molecule, [CHIM.COOR]Chemical Sciences/Coordination chemistry, General Materials Science, Counterion, Conformational isomerism
Abstract: International audience; Serendipitous self-assembly is a potential approach for achieving structurally versatile and unexpected solids with chosen metal–ligand combinations. Cyclen (1,4,7,10-tetraazacyclododecane) is an interesting flexible molecule, well explored for biological and material applications of its metal complexes. The dihedral angle (θ) between four nitrogen atoms of free cyclen is close to 0°. Still, it may vary upon complexation, allowing flexibility to adopt any two conformers, viz., (i) planar and (ii) twisted. The present work establishes the crucial role of metal ions in controlling the conformation adopted by cyclen through metal complexation. SCXRD studies of the complexes of cyclen with CuII and NiII with halides and pseudohalides as counterions reveal the existence of a planar conformation (θ = ∼0–3°) for cyclen in CuII systems and a highly twisted conformation (hitherto unreported) in NiII systems (θ = ∼52–55°). Further, SQUID magnetic studies for the dimeric [Ni1] complex reveal antiferromagnetic interactions between the two Ni centres.
Published: 2022
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3. Reentrant structural and optical properties of organic–inorganic hybrid metal cluster compound ((n-C4H9)4N)2[Mo6Bri8Bra6]

Author: Norio Saito, Daiki Nishiyama, Yoshitaka Matsushita, Yoshiki Wada, Stéphane Cordier, Takeo Ohsawa, Fabien Grasset, Naoki Ohashi, National Institute for Materials Science (NIMS), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratory for Innovative Key Materials and Structures (LINK), SAINT-GOBAIN-National Institute of Materials Science-Centre National de la Recherche Scientifique (CNRS), Materials Research Center for Element Strategy (MCES), Tokyo Tech, Saint-Gobain Company (Paris, France), CNRS Centre National de la Recherche Scientifique (CNRS) European Commission, Ministry of Education, Culture, Sports, Science and Technology via the Elemental Strategy Initiative Ministry of Education, Culture, Sports, Science and Technology, Japan (MEXT) [JPMXP0112101001], Saint-Gobain-National Institute of Materials Science-Centre National de la Recherche Scientifique (CNRS), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), 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: [CHIM]Chemical Sciences, General Materials Science, [CHIM.MATE]Chemical Sciences/Material chemistry, 02 engineering and technology, General Chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, 0210 nano-technology, Condensed Matter Physics, 01 natural sciences, 0104 chemical sciences
Abstract: International audience; We report the reentrant phase transition of the organic-inorganic hybrid metal cluster (MC) compound (TBA)(2)[(Mo6Br8Br6a)-Br-i] (TBA = ((n-C4H9)(4)N)). Structural studies revealed that (TBA)(2)[(Mo6Br8Br6a)-Br-i] was crystallized in the conventional monoclinic phase with space group P2(1)/n. When the crystal was cooled down to 143 K, we observed a structural phase transition from the conventional phase to an unknown phase with packing structure similar to the conventional one; however, the unit cell was extended to a double size. A reentrant transition to the conventional structure was induced when the crystal was further cooled to 113 K. These reentrant phase transitions occurred without any symmetry changes caused by slight motions of the MCs and TBA(+) ions. Luminescence studies revealed that the phase transition poorly affected the emission spectra; however, the newly found phase exhibited 1.7 times longer emission lifetime than the conventional phase. These results indicate that MC-based compounds are promising and exhibit phase transitions and crystallographic polymorphisms.
Published: 2022
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4. Alloying dichalcogenolate-protected Ag21 eight-electron nanoclusters: a DFT investigation

Author: Jean-Yves Saillard, Tzu-Hao Chiu, Samia Kahlal, Isaac Chantrenne, Jian-Hong Liao, Franck Gam, Chen-Wei Liu, 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), National Dong Hwa University (NDHU), France-Taiwan ANR-MOST 2018 program (project Nanoalloys), GENCI French National Computer Resource Center [A0030807367], Ministry of Science and Technology of TaiwanMinistry of Science and Technology, Taiwan [MOST 109-2113-M-259-008, 108-2923-M-259-001], ANR-18-CE09-0037,Nanoalloys,Alliages superatomiques et de structure précise riches en argent et en cuivre(2018), 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), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Valence (chemistry), Materials science, Icosahedral symmetry, Heteroatom, Doping, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, 0104 chemical sciences, Nanoclusters, Electronegativity, Crystallography, Atomic radius, [CHIM]Chemical Sciences, General Materials Science, 0210 nano-technology, Luminescence
Abstract: International audience; The isoelectronic doping of dichalcogenolato nanoclusters of the type [Ag-21{E2P(OR)(2)}(12)](+) (E = S, Se) by any heteroatom belonging to groups 9-12 was systematically investigated using DFT calculations. Although they can differ in their global structure, all of these species have the same M@M-12-centered icosahedral core. In any case, the different structure types are all very close in energy. In all of them, three different alloying sites can be identified (central, icosahedral, peripheral) and calculations allowed the trends in heteroatom site occupation preference across the group 9-12 family to be revealed. These trends are supported by complementary experimental results. They were rationalized on the basis of electronegativity, potential involvement in the bonding of valence d-orbitals and atom size. TD-DFT calculations showed that the effect of doping on optical properties is sizable and this should stimulate research on the modulation of luminescence properties in the dithiolato and diseleno families of complexes.
Published: 2022
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5. Dispiroacridine-indacenobisthiophene positional isomers: impact of the bridge on the physicochemical properties

Author: Bertrand Donnio, Jean-David Peltier, Joëlle Rault-Berthelot, Benoît Heinrich, Nicolas Leclerc, Cyril Poriel, Thomas Heiser, Olzhas A. Ibraikulov, 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 Physique et Chimie des Matériaux de Strasbourg (IPCMS), Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), Laboratoire des sciences de l'ingénieur, de l'informatique et de l'imagerie (ICube), École Nationale du Génie de l'Eau et de l'Environnement de Strasbourg (ENGEES)-Université de Strasbourg (UNISTRA)-Institut National des Sciences Appliquées - Strasbourg (INSA Strasbourg), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut National de Recherche en Informatique et en Automatique (Inria)-Les Hôpitaux Universitaires de Strasbourg (HUS)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Institut de chimie et procédés pour l'énergie, l'environnement et la santé (ICPEES), 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), Region Bretagne Region Bretagne, Agence de l'Environnement et de la Maitrise de l'Energie (ADEME), CNRS Centre National de la Recherche Scientifique (CNRS) European Commission, Universite de Strasbourg (UNISTRA), GENCI [2021-A0100805032], poriel, cyril, Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Strasbourg (UNISTRA)-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, 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), Institut National des Sciences Appliquées - Strasbourg (INSA Strasbourg), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-École Nationale du Génie de l'Eau et de l'Environnement de Strasbourg (ENGEES)-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)-Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-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)-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), 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), Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et nanosciences d'Alsace (FMNGE)
Subjects: Materials science, business.industry, 02 engineering and technology, Structural engineering, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Bridge (interpersonal), 0104 chemical sciences, [CHIM] Chemical Sciences, Materials Chemistry, Structural isomer, [CHIM]Chemical Sciences, General Materials Science, 0210 nano-technology, business
Abstract: International audience; We report the influence of positional isomerism on the electronic (electrochemical HOMO/LUMO energy levels), photophysical and physical properties (molecular organization, crystallinity and phase transitions) and charge transport properties of dispiroacridine-indacenobisthiophene positional isomers. The isomers differ from the central indacenobisthiophene (IDT) core, which displays either para or meta linkages. We show that the spiro-connected phenylacridine bridges have a significant influence on all these properties and particularly on the charge transport mobility values, which were found to be higher in the meta isomer than in the para isomer. This finding is different to what was reported in the literature for the other couples of IDT-based isomers and shows the key role played by the spiro-connected fragments in these molecular systems.
Published: 2022
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6. Additive-free selective methylation of secondary amines with formic acid over a Pd/In2O3 catalyst

Author: Caroline Genre, Idir Benaissa, Timothé Godou, Mathieu Pinault, 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-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Laboratoire Edifices Nanométriques (LEDNA), Fondation de la Maison de la Chimie (Paris, France), European Project: ERC CoG n°818260 ,ReNewHydrides, 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), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: 010405 organic chemistry, mental disorders, [CHIM.MATE]Chemical Sciences/Material chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, 010402 general chemistry, 01 natural sciences, Catalysis, 0104 chemical sciences, 3. Good health
Abstract: International audience; Formic acid is used as the sole carbon and hydrogen source in the methylation of aromatic and aliphatic amines to methylamines. The reaction proceeds via a formylation/transfer hydrogenation pathway over a solid Pd/In$_2$O$_3$ catalyst without the need for any additive.
Published: 2022
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7. Structure–Property–Function Relationships of Iron Oxide Multicore Nanoflowers in Magnetic Hyperthermia and Photothermia

Author: Enzo Bertuit, Emilia Benassai, Guillaume Mériguet, Jean-Marc Greneche, Benoit Baptiste, Sophie Neveu, Claire Wilhelm, Ali Abou-Hassan, PHysicochimie des Electrolytes et Nanosystèmes InterfaciauX (PHENIX), Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Institut des Molécules et Matériaux du Mans (IMMM), Le Mans Université (UM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de minéralogie, de physique des matériaux et de cosmochimie (IMPMC), Muséum national d'Histoire naturelle (MNHN)-Institut de recherche pour le développement [IRD] : UR206-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Laboratoire Physico-Chimie Curie [Institut Curie] (PCC), Institut Curie [Paris]-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), and ANR-18-CE09-0004,MicroNanoCell,Microfluidique Multi-échelle pour la Nanomédecine: de la synthèse haut débit de Nanoassemblages multifonctionnels, à leur BioTransformation et Remodelage Cellulaire dans des Conditions Biomimétiques Microfluidiques(2018)
Subjects: [PHYS]Physics [physics], magnetic nanoparticles, photothermia, Magnetic Phenomena, General Engineering, nanoflowers, General Physics and Astronomy, Hyperthermia, Induced, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, Ferric Compounds, 01 natural sciences, Ferrosoferric Oxide, nanothermal agents, 0104 chemical sciences, thermal therapies, General Materials Science, magnetic hyperthermia, multi-core iron oxides, 0210 nano-technology
Abstract: International audience; Magnetite and maghemite multi-core nanoflowers (NFs) synthesized using the modified polyol-mediated routes are to date among the most effective nano-heaters in magnetic hyperthermia (MHT). Recently, magnetite NFs have also shown high photothermal (PT) performances in the most desired second near infra-red (NIR-II) biological window making them attractive in the field of nanoparticle-activated thermal therapies. However, what makes 2 magnetic NFs efficient heating agents in both modalities still remain an open question. In this work, we investigate the role of many parameters of the polyol synthesis on the final NFs size, shape, chemical composition, number of cores and crystallinity. These nanofeatures are later correlated to the magnetic, optical and electronic properties of the NFs as well as their collective macroscopic thermal properties in MHT and PT to find relationships between their structure, properties and function. We evidence the critical role of iron(III) and heating ramps on the elaboration of well-defined NFs with high number of multi-cores. While MHT efficiency is found to be proportional to the average number of magnetic cores within the assemblies, the optical responses of the NFs and their collective photothermal properties depend directly on the mean volume of the NFs (as supported by optical cross sections numerical simulations) and strongly on the structural disorder in the NFs, rather than the stoichiometry. The concentration of defects in the nanostructures, evaluated by photoluminescence and Urbach energy (EU), evidences a switch in the optical behavior for a limit value of EU = 0.4 eV where a discontinuous transition from high to poor PT efficiency is also observed.
Published: 2021
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8. Stabilizing Interface between Li2S–P2S5 Glass-Ceramic Electrolyte and Ether Electrolyte by Tuning Solvation Reaction

Author: Bo Fan, Wenzhi Li, Zhongkuan Luo, Xianghua Zhang, Hongli Ma, Ping Fan, Bai Xue, Shenzhen University [Shenzhen], 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), The work is financially supported by the National Natural Science Foundation of China (NFSC) project (No. 51702216), the Natural Science Foundation of Guangdong Province (No. 2021A1515011725), the Stable Support Plan for Shenzhen Higher Education Institutions (No. 20200811211215001), the Shenzhen Science and Technology Foundation (JCYJ20210324095808023), and the State Key Laboratory of Silicon Materials Visiting Scholar Fund (SKL2020-10)., 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: hybrid electrolytes, 02 engineering and technology, lithium−sulfur batteries, 010402 general chemistry, 021001 nanoscience & nanotechnology, sulfide solid electrolyte, 01 natural sciences, 7. Clean energy, 0104 chemical sciences, Li2S−P2S5, interface, [CHIM]Chemical Sciences, General Materials Science, 0210 nano-technology
Abstract: International audience; Using solid-liquid hybrid electrolytes is an effective strategy to overcome the large solid/solid interfacial resistance in all-solid-state batteries and the safety problems in liquid batteries. The properties of the solid/liquid electrolyte interphase layer (SLEI) are essential for the performance of solid-liquid hybrid electrolytes. In this work, the solvation reactions between Li(2)S-P(2)S(5) glass-ceramic solid electrolytes (SEs) and ether electrolytes were studied, and their influence on the SLEI was examined. Although 1,2-dimethoxyethane (DME) reacted with the Li(2)S-P(2)S(5) glass-ceramic SE to form a dense SLEI, 1,3-dioxolane (DOL) severely corroded the SE, resulting in a loose SLEI. Consequently, a stable SLEI formed with DME. Using a combination of the Li(2)S-P(2)S(5) glass-ceramic SE and the DME-based liquid electrolyte (LE), stable lithium plating/stripping cycles over 1000 h and a hybrid Li-S battery that retained a specific capacity of 730 mAh g(-1) after 200 cycles were demonstrated. The knowledge of the reactions between the sulfide electrolytes and the organic LEs is instructive for the design of stable sulfide-liquid hybrid electrolytes for advanced batteries.
Published: 2021
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9. Chemical Design of IrS2 Polymorphs to Understand the Charge/Discharge Asymmetry in Anionic Redox Systems

Author: Thomas Marchandier, Sathiya Mariyappan, Artem M. Abakumov, Stéphane Jobic, Bernard Humbert, Jean-Yves Mevellec, Gwenaëlle Rousse, Maxim Avdeev, Rémi Dedryvère, Dominique Foix, Antonella Iadecola, Marie-Liesse Doublet, Jean-Marie Tarascon, Chimie du solide et de l'énergie (CSE), Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Skolkovo Institute of Science and Technology [Moscow] (Skoltech), 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), Nantes Université (Nantes Univ)-Nantes Université (Nantes Univ), Réseau sur le stockage électrochimique de l'énergie (RS2E), Aix Marseille Université (AMU)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-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 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)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Nantes Université (Nantes Univ)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), The University of Sydney, Australian Nuclear Science and Technology Organisation [Australie] (ANSTO), Institut des sciences analytiques et de physico-chimie pour l'environnement et les materiaux (IPREM), Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), 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), Collège de France - Chaire Chimie du solide et énergie, Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), U.S. Department of Energy under contract no. DE-AC02-06CH11357European Research Council (ERC) (FP/2014)/ERC grant/project no. 670116-ARPEMA, ANR-10-EQPX-0045,ROCK,Spectromètre EXAFS Rapide pour Cinétiques Chimiques(2010), Chaire Chimie du solide et énergie, Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-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 Paris - Chimie ParisTech-PSL (ENSCP), Université Fédérale Toulouse Midi-Pyrénées-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), and Sorbonne Université (SU)
Subjects: General Chemical Engineering, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], Materials Chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, 02 engineering and technology, General Chemistry, [CHIM.OTHE]Chemical Sciences/Other, 010402 general chemistry, 021001 nanoscience & nanotechnology, 0210 nano-technology, 01 natural sciences, 0104 chemical sciences
Abstract: International audience; Li-ion batteries are growing in demand and such growth calls for the quest for high-energy-density electrode materials. Li-rich layered oxides that show both cationic and anionic redox are expected to meet the high energy requirement. However, the oxygen anion activity triggers numerous structural and electronic rearrangements that need to be understood prior to envisioning applications. Here, we chemically design two new LixIrS2 polymorphs to further interrogate the mechanisms of the ligand redox process. By combined structural and spectroscopic characterizations, we show that electrochemical lithiation/delithiation of the polymorphs involve different sulfur redox couples that stand as unusual behavior. These structure-dependent kinetic pathways lead to an similar to 1 V difference between the two polymorphs, hence providing the missing link between the structure and hysteresis in anionic redox systems. These insights into the origin of hysteresis can guide proper parameters to cure it, hence laying the groundwork for the design of new practical electrode materials.
Published: 2021
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10. Evidence of the Ambipolar Behavior of Mo6 Cluster Iodides in All-Inorganic Solar Cells: A New Example of Nanoarchitectonic Concept

Author: Adèle Renaud, Pierre-Yves Jouan, Noée Dumait, Soraya Ababou-Girard, Nicolas Barreau, Tetsuo Uchikoshi, Fabien Grasset, Stéphane Jobic, Stéphane Cordier, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut 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), National Institute for Materials Science (NIMS), Laboratory for Innovative Key Materials and Structures (LINK), SAINT-GOBAIN-National Institute of Materials Science-Centre National de la Recherche Scientifique (CNRS), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Nantes (UN)-Université de Nantes (UN)-Ecole Polytechnique de l'Université de Nantes (EPUN), Université de Nantes (UN)-Université de Nantes (UN)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Physique de Rennes (IPR), Université de Rennes (UR)-Centre National de la Recherche Scientifique (CNRS), and Saint-Gobain-National Institute of Materials Science-Centre National de la Recherche Scientifique (CNRS)
Subjects: [CHIM.MATE]Chemical Sciences/Material chemistry, molybdenum octahedral cluster, 02 engineering and technology, electronic structure, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, 7. Clean energy, photoelectrochemistry, 0104 chemical sciences, solar cell, ambipolar material, [CHIM]Chemical Sciences, General Materials Science, 0210 nano-technology
Abstract: International audience; Ambipolar materials such as carbon nanotubes, graphene, or 2D transition metal chalcogenides are very attractive for a large range of applications, namely, light-emitting transistors, logic circuits, gas sensors, flash memories, and solar cells. In this work, it is shown that the nanoarchitectonics of inorganic Mo(6) cluster-based iodides enable to form thin films exhibiting photophysical properties that enable their classification as new members of the restricted family of ambipolar materials. Thus, the electronic properties of the ternary iodide Cs(2)[{Mo(6)I(8)(i)}I(6)(a)] and those of thin films of the aqua-complex-based compound [{Mo(6)I(8)(i)}I(4)(a)(H(2)O)(2)(a)]·xH(2)O were investigated through an in-depth photoelectrochemical study. Once hole/electron pairs are created, the holes and electrons turn to be transported simultaneously in opposite directions, and their lifetimes exhibit similar values. The ambipolar properties were demonstrated via the integration of [{Mo(6)I(8)(i)}I(4)(a)(H(2)O)(2)(a)]·xH(2)O as light harvesters in an all-solid solar cell. A significant photoresponse with a typical diode characteristic clearly provides evidence of the simultaneous transfer and transport of holes and electrons within the [{Mo(6)I(8)(i)}I(4)(a)(H(2)O)(2)(a)]·xH(2)O layer. The ambipolar behavior results, on the one hand, from the confinement of electrons imposed by the nanometric size of the molecular metal clusters and, on the other hand, from the poor electronic interactions between clusters in the solid state. Such molecular structure-based layers lead naturally to an intrinsic semiconducting behavior.
Published: 2021
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11. Stereoselective formation of bismuth complexes by transmetalation of lead with adaptable overhanging carboxylic acid 5,10-strapped porphyrins

Author: Thierry Roisnel, Stéphane Le Gac, Bernard Boitrel, Wael Barakat, Ismail Hijazi, Vincent Dorcet, 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), Lebanese University [Beirut] (LU), Région Bretagne is acknowledged for financial support to WB., 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: Steric effects, chemistry.chemical_classification, Transmetalation, Porphyrins, 010405 organic chemistry, Ligand, Metalation, Carboxylic acid, Supramolecular chemistry, Building and Construction, 010402 general chemistry, 01 natural sciences, Porphyrin, 0104 chemical sciences, chemistry.chemical_compound, Lead, chemistry, Coordination, Polymer chemistry, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Stereoselectivity, Electrical and Electronic Engineering, Bismuth
Abstract: International audience; Out-of-plane deformations of metalloporphyrin skeletons have been well documented as playing important roles in relevant biological processes. In contrast, out-of-plane binding to the N-core of large metal cations as period 6 post-transition elements has remained poorly investigated. We describe herein monometallic complexes of Pb(II) and Bi(III) with 5,10 single strapped porphyrin ligands bearing a carboxylic acid group with two possible “in/out” orientations, in which the metal ions are bound to the N-core of the macrocycle either from the strap side or from the naked side. In the case of Pb(II), both the kinetics of insertion and resulting OOP stereoselectivity are influenced by the “in/out” stereoisomerism of the overhanging COOH. Remarkably, Bi(III) insertion proceeded quasi-instantaneously at RT owing to the transmetalation of its Pb(II) counterpart. The addition of a cyano group in position of the carboxylic acid group generates a ligand exhibiting an increased stereoselectivity in the metalation processes with Pb(II) and Bi(III): these cations are coordinated exclusively from the naked and strap side of the macrocycle, respectively. This difference in behavior is likely explained by steric hindrance for the divalent cation, which is counterbalanced by the establishment of the second sphere of coordination with the strap for the trivalent cation. Such a behavior is thought of interest for the further design of adaptable supramolecular coordination assemblies.
Published: 2021
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12. Interstitial Nature of Mn2+ Doping in 2D Perovskites

Author: Andrew J. Torma, Wenbin Li, Hao Zhang, Qing Tu, Vladislav V. Klepov, Michael C. Brennan, Christopher L. McCleese, Matthew D. Krzyaniak, Michael R. Wasielewski, Claudine Katan, Jacky Even, Martin V. Holt, Tod A. Grusenmeyer, Jie Jiang, Ruth Pachter, Mercouri G. Kanatzidis, Jean-Christophe Blancon, Aditya D. Mohite, Rice University [Houston], Texas A&M University [College Station], Northwestern University [Evanston], Air Force Research Laboratory (AFRL), United States Air Force (USAF), 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), Institut des Fonctions Optiques pour les Technologies de l'informatiON (Institut FOTON), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-École Nationale Supérieure des Sciences Appliquées et de Technologie (ENSSAT)-Centre National de la Recherche Scientifique (CNRS)-IMT Atlantique Bretagne-Pays de la Loire (IMT Atlantique), Institut Mines-Télécom [Paris] (IMT)-Institut Mines-Télécom [Paris] (IMT), Argonne National Laboratory [Lemont] (ANL), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-École Nationale Supérieure des Sciences Appliquées et de Technologie (ENSSAT)-Centre National de la Recherche Scientifique (CNRS), FA8650-16-D-5402-0001, Air Force Research Laboratory, Army Research Office, DE-FG02-99ER14999, Basic Energy Sciences, Texas A and M Engineering Experiment Station, Texas A and M University, Institut Universitaire de France, 20-587, National Science Foundation, and Triads for Transformation, Texas A and M University
Subjects: [PHYS]Physics [physics], crystal structure, strain mapping, General Engineering, General Physics and Astronomy, doping, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, nano X-ray diffraction, 01 natural sciences, transition metals, 0104 chemical sciences, Condensed Matter::Materials Science, halide perovskites, [CHIM]Chemical Sciences, Condensed Matter::Strongly Correlated Electrons, General Materials Science, 0210 nano-technology, density functional theory, ComputingMilieux_MISCELLANEOUS
Abstract: International audience; Halide perovskites doped with magnetic impurities (such as the transition metals Mn2+, Co2+, Ni2+) are being explored for a wide range of applications beyond photovoltaics, such as spintronic devices, stable light-emitting diodes, single-photon emitters, and magneto-optical devices. However, despite several recent studies, there is no consensus on whether the doped magnetic ions will predominantly replace the octahedral B-site metal via substitution or reside at interstitial defect sites. Here, by performing correlated nanoscale X-ray microscopy, spatially and temporally resolved photoluminescence measurements, and magnetic force microscopy on the inorganic 2D perovskite Cs2PbI2Cl2, we show that doping Mn2+ into the structure results in a lattice expansion. The observed lattice expansion contrasts with the predicted contraction expected to arise from the B-site metal substitution, thus implying that Mn2+ does not replace the Pb2+ sites. Photoluminescence and electron paramagnetic resonance measurements confirm the presence of Mn2+ in the lattice, while correlated nano-XRD and X-ray fluorescence track the local strain and chemical composition. Density functional theory calculations predict that Mn2+ atoms reside at the interstitial sites between two octahedra in the triangle formed by one Cl– and two I– atoms, which results in a locally expanded structure. These measurements show the fate of the transition metal dopants, the local structure, and optical emission when they are doped at dilute concentrations into a wide band gap semiconductor.
Published: 2021
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13. Synthesis of Heterospirocycles through Gold‐(I) Catalysis: Useful Building Blocks for Medicinal Chemistry

Author: Kossi Efouako Soklou, Hamid Marzag, Karen Plé, Sylvain Routier, Béatrice Vallée, 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), Centre de biophysique moléculaire (CBM), 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), PLE, Karen, 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), and Université d'Orléans (UO)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)
Subjects: [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Chemistry, Nitrogen heterocycles, [CHIM.THER] Chemical Sciences/Medicinal Chemistry, Molecular Diversity, Gold catalysis, [CHIM.THER]Chemical Sciences/Medicinal Chemistry, General Chemistry, [CHIM.ORGA] Chemical Sciences/Organic chemistry, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Catalysis, Synthetic methods, Organic chemistry, Spiro Compounds
Abstract: International audience; Gold-(I) catalysis was used for the intramolecular cyclization of tertiary alcohols with terminal alkynes to form diverse aza-spirocycles. The reaction was carried out with low catalyst loading under microwave irradiation to give both sulfonylated and acylated spirocyclic nitrogen derivatives. Gram scale spirocyclization was carried out and demonstrates the robustness of the reaction. An intramolecular Mizoroki-Heck reaction was performed to give several tetracyclic spirocycles. Double bond reduction and selective protecting group manipulation gave spiropiperazine and spiromorpholine derivatives. These compounds were incorporated into biologically relevant scaffolds to give the first selective spirocyclic inhibitors of LIMK.
Published: 2021
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14. Unlocking the Friedel-Crafts arylation of primary aliphatic alcohols and epoxides driven by hexafluoroisopropanol

Author: Andrei Golushko, Florent Noël, Shaofei Zhang, Marie Vayer, Nazanin Rezajooei, Christopher N. Rowley, Vuk D. Vuković, Joseph Moran, David Lebœuf, 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), Department of Chemistry, Memorial University of Newfoundland, St. John's, Canada, Memorial University of Newfoundland [St. John's], Carleton University, univOAK, Archive ouverte, 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, 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), and Memorial University of Newfoundland = Université Memorial de Terre-Neuve [St. John's, Canada] (MUN)
Subjects: [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, General Chemical Engineering, Biochemistry (medical), [CHIM.CATA] Chemical Sciences/Catalysis, Alcohol, [CHIM.CATA]Chemical Sciences/Catalysis, General Chemistry, Alkylation, [CHIM.ORGA] Chemical Sciences/Organic chemistry, 010402 general chemistry, 01 natural sciences, Biochemistry, 0104 chemical sciences, Catalysis, chemistry.chemical_compound, chemistry, Electrophile, Materials Chemistry, Nucleophilic substitution, Environmental Chemistry, Organic chemistry, SN2 reaction, Brønsted–Lowry acid–base theory, Friedel–Crafts reaction
Abstract: International audience; Alcohols and epoxides are arguably ideal electrophiles for the Friedel-Crafts alkylation, since they are widely available, require no pre-activation, and produce no stoichiometric waste beyond water. However, neither primary aliphatic alcohols nor most classes of terminal epoxides are compatible with existing intermolecular Friedel-Crafts methodologies, and sequential Friedel-Crafts reactions starting from epoxides consequently remain underexplored. Here, we report that these limitations are easily overcome using Brønsted acid catalysis in hexafluoroisopropanol (HFIP) as a solvent. Electron-poor aromatic epoxides and aliphatic epoxides undergo stereospecific arylation to give an alcohol which, depending on the reaction conditions, can partake in a second nucleophilic substitution with a different arene in one pot. Phenyl ethanols react through a phenonium intermediate, whereas simple aliphatic alcohols participate in a rare intermolecular SN2 Friedel-Crafts process, delivering linear products exclusively. This work provides an alternative to metal-catalyzed cross-couplings for accessing important scaffolds, widening the range of applications of the Friedel-Crafts reaction
Published: 2021
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15. Enhancement of microbial fuel cell efficiency by incorporation of graphene oxide and functionalized graphene oxide in sulfonated polyethersulfone membrane

Author: Anthony Szymczyk, Mehri Shabani, Ahmad Rahimpour, Maxime Pontié, Hanxiao Guo, Mostafa Rahimnejad, Habibollah Younesi, Tarbiat Modares University [Tehran], ESAIP, Université d'Angers (UA), Babol Noshirvani University of Technology, 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), Iran National Science Foundation, INSF: 97014305, IG-39804, Campus France, Tarbiat Modares University, TMU, Universite Angers, 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: Microbial fuel cell, Materials science, Oxide, 02 engineering and technology, Conductivity, 010402 general chemistry, 01 natural sciences, law.invention, chemistry.chemical_compound, law, Functionalized GO, [CHIM]Chemical Sciences, Electricity generation, Renewable Energy, Sustainability and the Environment, Graphene, Proton exchange membranes, 021001 nanoscience & nanotechnology, Polyelectrolyte, 0104 chemical sciences, Membrane, chemistry, Chemical engineering, 0210 nano-technology, Selectivity, Faraday efficiency
Abstract: International audience; The present work examines, for the first time, the use of thiolated graphene oxide (TGO), in polyelectrolyte composite membranes as an effective approach to enhance the MFC performance. A new composite membrane based on a sulfonated polyethersulfone (SPES) hybrid with GO, sulfonated GO (SGO), and TGO was fabricated and assessed in MFC. The blend membranes were characterized with various techniques. The sulfhydryl (-SH) and sulfonic (-SO3H) groups enhanced the proton selectivity of the membrane and MFC performance. The MFC using the SPES/SGO1.8% composite membrane generated a power density of 66.4 mW/m2 which was double that produced by MFC using Nafion117 membrane in batch mode which lasted for 8 days. The SPES/SGO membrane was more selective towards H+ rather than other cations (K+, Na+, and Li+). This was also confirmed by the results of proton conductivity analysis, as the SPES/SGO1.8% membranes showed a value of 1.42 mS/cm which was higher than Nafion117 (1.3 mS/cm), SPES/TGO1.8% (1.25 mS/cm), SPES/GO1.8% (0.56 mS/cm), and SPES (0.32 mS/cm). The higher COD removal and coulombic efficiency were obtained in MFC with SPES/SGO membranes. In conclusion, it is our view that the new SPES/SGO and SPES/TGO membranes can be applied favorably in dual-chamber MFCs meeting their needs. © 2021 Elsevier Ltd
Published: 2021
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16. The Role of (tBuPOCOP)Ir(I) and Iridium(III) Pincer Complexes in the Catalytic Hydrogenolysis of Silyl Triflates into Hydrosilanes

Author: Gabriel Durin, Thibault Cantat, Emmanuel Nicolas, Pierre Thuéry, Jean-Claude Berthet, 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), For financial support of this work, we acknowledge CEA, CNRS, the University Paris-Saclay, CINES (HPC Computing time on Occigen, grant no. A0080806494)., European Project: ERC CoG n°818260 ,ReNewHydrides, Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), CINES (HPC Computing time on Occigen, grant no.A0100806494, and Fondation Louis D.−Institut de France
Subjects: Silylation, chemistry.chemical_element, Crystal structure, Iridium, Hydrosilanes, 010402 general chemistry, 01 natural sciences, Medicinal chemistry, Catalysis, Inorganic Chemistry, POCOP, chemistry.chemical_compound, Hydrogenolysis, Physical and Theoretical Chemistry, Reduction, 010405 organic chemistry, Hydride, Organic Chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, 0104 chemical sciences, Pincer movement, Pincer Complexes, chemistry, Silyl Triflates
Abstract: International audience; Hydrosilanes are convenient reductants for a large variety of organic substrates, but they are produced via energy-intensive processes. These limitations call for the development of general catalytic processes able to transform Si–O into Si–H bonds. We report here the catalytic hydrogenolysis of R$_3$SiOTf (R = Me, Et, and Ph) species in the presence of a base (e.g., NEt$_3$), by the hydride complexes [($^{tBu}$POCOP)IrH(X)] (X = H and OTf; ($^{tBu}$POCOP = [1,3-C$_6$H$_3$)(OPtBu)$_2$]). Syntheses and crystal structures of new iridium(I) and iridium(III) complexes are presented as well as their role in the R$_3$SiOTf to R$_3$SiH transformation. The mechanisms of these reactions have been examined by DFT studies, revealing that the active species involved in the reduction of the Si–OTf vs Si–Cl bond are different. The rate-determining transition state is a base-assisted splitting of H$_2$, forming an iridium(III) dihydride species.
Published: 2021
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17. Greening Pathways for Synthetic Talc Production Based on the Supercritical Hydrothermal Flow Process

Author: Jubayed, François Martin, Guido Sonnemann, Marie Claverie, Valentina Musumeci, Edis Glogic, Cyril Aymonier, Christel Carême, Institut des Sciences Moléculaires (ISM), 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), 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), Imerys Talc Europe, IMERYS, Department of Mechanical Engineering, University of Coimbra [Portugal] (UC), Géosciences Environnement Toulouse (GET), Institut national des sciences de l'Univers (INSU - CNRS)-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-Université Fédérale Toulouse Midi-Pyrénées-Observatoire Midi-Pyrénées (OMP), Météo France-Centre National d'Études Spatiales [Toulouse] (CNES)-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Météo France-Centre National d'Études Spatiales [Toulouse] (CNES)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD), The University of Bordeaux, and the French National Center for Scientific Research, as well as the Conseil Régional Nouvelle-Aquitaine for the financial support., Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1 (UB)-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Imerys Aluminates, Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire Midi-Pyrénées (OMP), and Université de Toulouse (UT)-Université de Toulouse (UT)-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National d'Études Spatiales [Toulouse] (CNES)-Centre National de la Recherche Scientifique (CNRS)-Météo-France -Institut de Recherche pour le Développement (IRD)-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National d'Études Spatiales [Toulouse] (CNES)-Centre National de la Recherche Scientifique (CNRS)-Météo-France -Centre National de la Recherche Scientifique (CNRS)
Subjects: Materials science, General Chemical Engineering, 02 engineering and technology, 010402 general chemistry, Talc, 7. Clean energy, 01 natural sciences, Hydrothermal circulation, Greening, life cycle assessment, supercritical hydrothermal flow synthesis, medicine, Environmental Chemistry, Flow process, Renewable Energy, Sustainability and the Environment, synthetic talc, [CHIM.MATE]Chemical Sciences/Material chemistry, General Chemistry, 021001 nanoscience & nanotechnology, Supercritical fluid, 0104 chemical sciences, precursor concentration, ex ante LCA, Chemical engineering, 13. Climate action, Scientific method, 0210 nano-technology, medicine.drug
Abstract: International audience; Recent efforts in chemistry have led to development of a fast and continuous process for the production of synthetic talc in a supercritical hydrothermal reactor. This attractive process compatible with industrial requirements leads to advantageous physicochemical characteristics including submicrometer size, hydrophilicity, and high chemical and mineralogical purity. In addition, the high speed of the process and moderate reaction conditions have potential advantages from a viewpoint of the impacts on the environment. To verify environmental advantages and seize further opportunities to improve environmental performance, the current study evaluates the new process using the life cycle assessment (LCA) methodology. A cradle-to-gate assessment considers the production of synthetic talc from different magnesium and reagent acid precursors at different concentrations. The findings suggest high impacts of precursors (65–94%, depending on their concentration) and low impacts of process energy and water. Substituting magnesium acetate with magnesium sulfate could reduce greenhouse gases from 4.8 to 2.6 kgCO2 and cumulative energy use from 86 to 34 MJ per 1 kg of synthetic talc. Discussion draws on previous LCA studies on the supercritical hydrothermal process and applications of synthetic talc considering its environmental performance and characteristics in comparison to the conventional (natural) talc.
Published: 2021
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18. Quantifying Image Charge Effects in Molecular Tunnel Junctions Based on Self-Assembled Monolayers of Substituted Oligophenylene Ethynylene Dithiols

Author: Olivier Galangau, Quyen Van Nguyen, C. Daniel Frisbie, Jérôme Cornil, Zuoti Xie, Lucie Norel, Sandra Rodriguez-Gonzalez, Stéphane Rigaut, Valentin Diez Cabanes, Guangdong University of Technology, Technion - Israel Institute of Technology [Haifa], University of Minnesota System, University of Mons [Belgium] (UMONS), Universidad de Málaga [Málaga] = University of Málaga [Málaga], 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), C.D.F. acknowledges financial support from the U.S. National Science Foundation (CHE-2003199). Parts of this work were carried out in the Characterization Facility, University of Minnesota, which receives partial support from NSF through the MRSEC program (DMR-2011401). The work of S.R.G. has been supported by the Belgian National Fund for Scientific Research (F.R.S.-FNRS). We also acknowledge the Consortium des Équipements de Calcul Intensif (CÉCI) funded by F.R.S.-FNRSfor providing the computational resources. J.C. is an FNRS research director., Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), 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: Materials science, image charge, photoelectron spectroscopy, 02 engineering and technology, 010402 general chemistry, Method of image charges, 01 natural sciences, Molecular physics, symbols.namesake, tunneling, [CHIM]Chemical Sciences, General Materials Science, single level model, HOMO/LUMO, Quantum tunnelling, Fermi level-HOMO offset, Fermi level, Self-assembled monolayer, 021001 nanoscience & nanotechnology, Potential energy, charge transport, 0104 chemical sciences, Specific orbital energy, symbols, Density functional theory, 0210 nano-technology, molecular junction
Abstract: International audience; A number of factors contribute to orbital energy alignment with respect to the Fermi level in molecular tunnel junctions. Here, we report a combined experimental and theoretical effort to quantify the effect of metal image potentials on the highest occupied molecular orbital to Fermi level offset, ε(h), for molecular junctions based on self-assembled monolayers (SAMs) of oligophenylene ethynylene dithiols (OPX) on Au. Our experimental approach involves the use of both transport and photoelectron spectroscopy to extract the offsets, ε(h)(trans) and ε(h)(UPS), respectively. We take the difference in these quantities to be the image potential energy eV(image). In the theoretical approach, we use density functional theory (DFT) to calculate directly eV(image) between positive charge on an OPX molecule and the negative image charge in the Au. Both approaches yield eV(image) ∼ -0.1 eV per metal contact, meaning that the total image potential energy is ∼-0.2 eV for an assembled junction with two Au contacts. Thus, we find that the total image potential energy is 25-30% of the total offset ε(h), which means that image charge effects are significant in OPX junctions. Our methods should be generally applicable to understanding image charge effects as a function of molecular size, for example, in a variety of SAM-based junctions.
Published: 2021
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19. Carbon Dioxide Reduction: A Bioinspired Catalysis Approach

Author: Yun Li, Thibault Fogeron, Maria Gómez-Mingot, Marc Fontecave, Laboratoire de Chimie des Processus Biologiques (LCPB), Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Chaire Chimie des processus biologiques, and Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)
Subjects: 010405 organic chemistry, Chemistry, Ligand, Molybdopterin, Context (language use), General Medicine, General Chemistry, Carbon Dioxide, 010402 general chemistry, Formate Dehydrogenases, 01 natural sciences, Combinatorial chemistry, Catalysis, 0104 chemical sciences, chemistry.chemical_compound, 13. Climate action, Pyran, Catalytic Domain, [CHIM]Chemical Sciences, Chelation, Sulfur, Organometallic chemistry, Electrochemical reduction of carbon dioxide
Abstract: ConspectusWhile developed in a number of directions, bioinspired catalysis has been explored only very recently for CO2 reduction, a challenging reaction of prime importance in the context of the energetic transition to be built up. This approach is particularly relevant because nature teaches us that CO2 reduction is possible, with low overpotentials, high rates, and large selectivity, and gives us unique clues to design and discover new interesting molecular catalysts. Indeed, on the basis of our relatively advanced understanding of the structures and mechanisms of the active sites of fascinating metalloenzymes such as formate dehydrogenases (FDHs) and CO dehydrogenases (CODHs), it is possible to design original, active, selective, and stable molecular catalysts using the bioinspired approach. These metalloenzymes use fascinating metal centers: in FDHs, a Mo(W) mononuclear ion is coordinated by four sulfur atoms provided by a specific organic ligand, molybdopterin (MPT), containing a pyranopterin heterocycle (composed of a pyran ring fused with a pterin unit) and two sulfhydryl groups for metal chelation; in CODHs, catalytic activity depends on either a unique nickel-iron-sulfur cluster or a dinuclear Mo-Cu complex in which the Mo ion is chelated by an MPT ligand. As a consequence, the novel class of catalysts, designed by bioinspiration, consists of mononuclear Mo, W, and Ni and as well as dinuclear Mo-Cu and Ni-Fe complexes in which the metal ions are coordinated by sulfur ligands, more specifically, dithiolene chelates mimicking the natural MPT cofactor. In general, their activity is evaluated in electrochemical systems (cyclic voltammetry and bulk electrolysis) or in photochemical systems (in the presence of a photosensitizer and a sacrificial electron donor) in solution. This research is multidisciplinary because it implies detailed biochemical, functional, and structural characterization of the inspiring enzymes together with synthetic organic and organometallic chemistry and molecular catalysis studies. The most important achievements in this direction, starting from the first report of a catalytically active biomimetic bis-dithiolene-Mo complex in 2015, are discussed in this Account, highlighting the challenging issues associated with synthesis of such sophisticated ligands and molecular catalysts as well as the complexity of reaction mechanisms. While the very first active biomimetic catalysts require further improvement, in terms of performance, they set the stage in which molecular chemistry and enzymology can synergistically cooperate for a better understanding of why nature has selected these sites and for developing highly active catalysts.
Published: 2021
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20. A Copper(I)‐Catalyzed Sulfonylative Hiyama Cross‐Coupling

Author: Adenot, Aurélien, Anthore-Dalion, Lucile, Nicolas, Emmanuel, Berthet, Jean-Claude, Thuéry, Pierre, Cantat, Thibault, Berthet, Jean‐claude, 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), GENCI for computing time (Allocation n°A0100806494), Institut de France, European Project: ERC CoG n°818260 ,ReNewHydrides, Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut Rayonnement Matière de Saclay (IRAMIS), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)
Subjects: High energy, Reaction mechanism, chemistry.chemical_element, 010402 general chemistry, 01 natural sciences, Reductive elimination, Catalysis, chemistry.chemical_compound, Polymer chemistry, Molecule, Coupling, Silanes, 010405 organic chemistry, Aryl, Organic Chemistry, Esters, [CHIM.CATA]Chemical Sciences/Catalysis, General Chemistry, Ketones, Copper, 0104 chemical sciences, Coupling (electronics), chemistry
Abstract: International audience; An air-tolerant Cu-catalyzed sulfonylative Hiyama cross-coupling reaction enabling the formation of diaryl sulfones is described. Starting from aryl silanes, DABSO and aryliodides, the reaction tolerates a large variety of polar functional groups (amines, ketones, esters, aldehydes). Control experiments coupled with DFT calculations shed light on the mechanism, characterized by the formation of a Cu(I)-sulfinate intermediate via fast insertion of a SO$_2$ molecule.
Published: 2021
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21. Adhesion Behavior of Ti–PMMA–Ti Sandwiches for Biomedical Applications

Author: Patrick Masson, Flavien Mouillard, Geneviève Pourroy, Adele Carradò, Gargi Shankar Nayak, Heinz Palkowski, Clausthal University of Technology (TU Clausthal), Institut de Physique et Chimie des Matériaux de Strasbourg (IPCMS), Université de Strasbourg (UNISTRA)-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, 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 Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), and MASSON, Patrick
Subjects: Materials science, article, technology, industry, and agriculture, General Engineering, macromolecular substances, 02 engineering and technology, Adhesion, equipment and supplies, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, 0104 chemical sciences, body regions, [CHIM] Chemical Sciences, [CHIM]Chemical Sciences, General Materials Science, Composite material, 0210 nano-technology, ddc:600
Abstract: The “stress-shielding” problem, common with metallic implants, may be solved by using biocompatible sandwiches with a polymeric core between two metallic skin sheets. To achieve such sandwiches, a process route has been developed, beginning with the grafting of poly-(methyl-methacrylate) (PMMA) on titanium (Ti) sheets via the “grafting from” technique. Grafting resulted in variable thicknesses of PMMA on the Ti sheets. Hot-pressing was used to prepare semi-finished Ti–PMMA–Ti sandwiches. The adhesion was achieved by the interpenetration between PMMA sheet and the grafted PMMA chains. Investigation was carried out to understand the influence of the grafted PMMA thickness on the adhesion strength. Similar adhesion strengths were found for the sandwiches despite variable grafted PMMA thicknesses, indicating a successful grafting of PMMA on large-scale Ti sheets. The adhesion followed the autohesion theory, where a time-dependent increase in adhesion strength was found for the sandwiches.
Published: 2021
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22. Synthesis of a Negative Photochrome with High Switching Quantum Yields and Capable of Singlet‐Oxygen Production and Storage

Author: Christian Philouze, Guy Royal, Martial Boggio-Pasqua, Elise Lognon, Frédérique Loiseau, Saioa Cobo, Zakaria Ziani, 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), Laboratoire de Chimie et Physique Quantiques Laboratoire (LCPQ), 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)-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)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS), and ANR-18-CE29-0012,Photochromics,Architectures Moléculaires Multi-Photochromes Innovantes pour la Production de NO et 1O2(2018)
Subjects: 010405 organic chemistry, Singlet oxygen, Organic Chemistry, Quantum yield, General Chemistry, 010402 general chemistry, Photochemistry, Triphenylamine, 01 natural sciences, 7. Clean energy, Acceptor, Catalysis, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Photochromism, chemistry.chemical_compound, chemistry, Cyclic voltammetry, Methylpyridinium, Absorption (electromagnetic radiation)
Abstract: International audience; A dimethyldihydropyrene (DHP) photochromic unit has been functionalized by donor (triphenylamine group) and acceptor (methyl-pyridinium) substituents. This compound was characterized by NMR, absorption and emission spectroscopies as well as cyclic voltammetry and its properties were rationalized by theoretical calculations. The incorporation of both electron donor and withdrawing groups on the photochromic center allows i) an efficient photo-isomerization of the system when illuminated at low energy (quantum yield: Фc-o = 13.3% at λex.= 660 nm), ii) the reversible and quantitative formation of two endoperoxyde isomers when illuminated under aerobic conditions at room temperature and iii) the storage and production of singlet oxygen. The photo-isomerization mechanism was also investigated by spin-flip TD-DFT (SF-TD-DFT) calculations.
Published: 2021
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23. Mn-Doped Quinary Ag–In–Ga–Zn–S Quantum Dots for Dual-Modal Imaging

Author: Raphaël Schneider, Bolat Uralbekov, Perizat Galiyeva, Jordane Jasniewski, Halima Alem, Sébastien Leclerc, Sébastien Blanchard, Hervé Rinnert, Ghouti Medjahdi, Sabine Bouguet-Bonnet, Lavinia Balan, Laboratoire Réactions et Génie des Procédés (LRGP), Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS), Institut Jean Lamour (IJL), Université de Lorraine (UL)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Cristallographie, Résonance Magnétique et Modélisations (CRM2), Laboratoire Énergies et Mécanique Théorique et Appliquée (LEMTA ), Conditions Extrêmes et Matériaux : Haute Température et Irradiation (CEMHTI), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université d'Orléans (UO), 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 d'Ingénierie des Biomolécules (LIBio), Université de Lorraine (UL), Al-Farabi Kazakh National University [Almaty] (KazNU), IMPACT Biomolécules, and ANR-15-IDEX-0004,LUE,Isite LUE(2015)
Subjects: Materials science, General Chemical Engineering, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Article, [SPI.MECA.MEFL]Engineering Sciences [physics]/Mechanics [physics.med-ph]/Fluids mechanics [physics.class-ph], Condensed Matter::Materials Science, Semiconductor quantum dots, Transition metal, Condensed Matter::Superconductivity, Mn doped, QD1-999, business.industry, Doping, Quinary, General Chemistry, Condensed Matter::Mesoscopic Systems and Quantum Hall Effect, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Dual (category theory), [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Chemistry, Modal, Quantum dot, Optoelectronics, Condensed Matter::Strongly Correlated Electrons, 0210 nano-technology, business
Abstract: International audience; Doping of transition metals within a semiconductor quantum dot (QD) has a high impact on the optical and magnetic properties of the QD. In this study, we report the synthesis of Mn 2+-doped Ag−In−Ga−Zn−S (Mn:AIGZS) QDs via thermolysis of a dithiocarbamate complex of Ag + , In 3+ , Ga 3+ , and Zn 2+ and of Mn(stearate) 2 in oleylamine. The influence of the Mn 2+ loading on the photoluminescence (PL) and magnetic properties of the dots are investigated. Mn:AIGZS QDs exhibit a diameter of ca. 2 nm, a high PL quantum yield (up to 41.3% for a 2.5% doping in Mn 2+), and robust photo-and colloidal stabilities. The optical properties of Mn:AIGZS QDs are preserved upon transfer into water using the glutathione tetramethylammonium ligand. At the same time, Mn:AIGZS QDs exhibit high relaxivity (r 1 = 0.15 mM −1 s −1 and r 2 = 0.57 mM −1 s −1 at 298 K and 2.34 T), which shows their potential applicability for bimodal PL/magnetic resonance imaging (MRI) probes.
Published: 2021
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24. How do H2 oxidation molecular catalysts assemble onto carbon nanotube electrodes? A crosstalk between electrochemical and multi-physical characterization techniques†

Author: Sandrine Lyonnard, Laura Calvillo, Bertrand Reuillard, Laure Guétaz, Hanako Okuno, Vincent Artero, Gaetano Granozzi, Ahmed Ghedjatti, Nathan Coutard, Pascale Chenevier, Solar fuels, hydrogen and catalysis (SolHyCat), Laboratoire de Chimie et Biologie des Métaux (LCBM - UMR 5249), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA), Laboratoire d'Etude des Matériaux par Microscopie Avancée (LEMMA ), Modélisation et Exploration des Matériaux (MEM), Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), SYstèmes Moléculaires et nanoMatériaux pour l’Energie et la Santé (SYMMES), Università degli Studi di Padova = University of Padua (Unipd), Département des Technologies des NanoMatériaux (DTNM), Laboratoire d'Innovation pour les Technologies des Energies Nouvelles et les nanomatériaux (LITEN), Institut National de L'Energie Solaire (INES), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS)-Institut National de L'Energie Solaire (INES), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS), Synthèse, Structure et Propriétés de Matériaux Fonctionnels (STEP ), ANR-17-EURE-0003,CBH-EUR-GS,CBH-EUR-GS(2017), Department of Chemical Sciences, University of Padova, Centre National de la Recherche Scientifique (CNRS)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut National de L'Energie Solaire (INES), and Centre National de la Recherche Scientifique (CNRS)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)
Subjects: Materials science, Nanostructure, Nanotechnology, 02 engineering and technology, Carbon nanotube, engineering.material, 010402 general chemistry, Electrochemistry, 01 natural sciences, 7. Clean energy, Catalysis, law.invention, Coating, law, Monolayer, General Chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, Small-angle neutron scattering, 0104 chemical sciences, [SPI.TRON]Engineering Sciences [physics]/Electronics, Chemistry, Transmission electron microscopy, engineering, 0210 nano-technology
Abstract: Molecular catalysts show powerful catalytic efficiency and unsurpassed selectivity in many reactions of interest. As their implementation in electrocatalytic devices requires their immobilization onto a conductive support, controlling the grafting chemistry and its impact on their distribution at the surface of this support within the catalytic layer is key to enhancing and stabilizing the current they produce. This study focuses on molecular bioinspired nickel catalysts for hydrogen oxidation, bound to carbon nanotubes, a conductive support with high specific area. We couple advanced analysis by transmission electron microscopy (TEM), for direct imaging of the catalyst layer on individual nanotubes, and small angle neutron scattering (SANS), for indirect observation of structural features in a relevant aqueous medium. Low-dose TEM imaging shows a homogeneous, mobile coverage of catalysts, likely as a monolayer coating the nanotubes, while SANS unveils a regular nanostructure in the catalyst distribution on the surface with agglomerates that could be imaged by TEM upon aging. Together, electrochemistry, TEM and SANS analyses allowed drawing an unprecedented and intriguing picture with molecular catalysts evenly distributed at the nanoscale in two different populations required for optimal catalytic performance., How do efficient hydrogen-oxidation molecular electrocatalysts connect onto their carbon nanotube conductive support? A coupled neutron scattering SANS and STEM electron microscopy study to observe soft active matter organizing on 3D nanosurfaces.
Published: 2021
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25. Open-air printing of Cu2O thin films with high hole mobility for semitransparent solar harvesters

Author: Abderrahime Sekkat, César Masse de la Huerta, Guy Chichignoud, Daniel Bellet, Anne Kaminski-Cachopo, Laetitia Rapenne, David Muñoz-Rojas, Viet Huong Nguyen, Laboratoire des matériaux et du génie physique (LMGP ), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA), Institut de Microélectronique, Electromagnétisme et Photonique - Laboratoire d'Hyperfréquences et Caractérisation (IMEP-LAHC), Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA), Science et Ingénierie des Matériaux et Procédés (SIMaP), and Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )
Subjects: Electron mobility, Fabrication, Materials science, business.industry, Band gap, Photovoltaic system, [CHIM.MATE]Chemical Sciences/Material chemistry, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, 7. Clean energy, 01 natural sciences, 0104 chemical sciences, Atomic layer deposition, Semiconductor, Mechanics of Materials, Photovoltaics, TA401-492, Optoelectronics, General Materials Science, Thin film, 0210 nano-technology, business, Materials of engineering and construction. Mechanics of materials
Abstract: Cu2O is a promising p-type semiconductor for low-cost photovoltaics and transparent optoelectronics. However, low-cost and low-temperature fabrication of Cu2O films with good transport properties remains challenging, thus limiting their widespread adoption in devices. Here, we report Cu2O thin films of 20–80 nm thickness with hole mobility up to 92 cm2V−1s−1 using atmospheric-pressure spatial atomic layer deposition at temperatures below 260 °C, from a copper (I) hexafluoro-2,4-pentanedionate cyclooctadiene precursor. Raman spectroscopy indicates the presence of copper split vacancies and shows that the high hole mobility can be correlated to a low concentration of shallow acceptor defects. The optical bandgap of deposited films can be tuned between 2.08 eV and 2.5 eV, depending on the deposition temperature. All-oxide semitransparent Cu2O/ZnO solar harvesters are fabricated, showing efficiency values comparable to devices that incorporate much thicker Cu2O layers. Our work provides a promising approach towards cost-efficient, all-oxide solar harvesters, and for other (opto)electronic devices. Semiconducting Cu2O is attractive for photovoltaic and optoelectronic devices, though balancing high hole mobility with low-cost fabrication is challenging. Here, Cu2O thin films with high hole mobility of 92 cm²V−1s−1 are deposited in air, and applied in a semi-transparent solar harvester.
Published: 2023
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26. Click and Bioorthogonal Chemistry: The Future of Active Targeting of Nanoparticles for Nanomedicines?

Author: Carole Chaix, Emmanuel Moreau, Carole Farre, Ludivine Taiariol, Imagerie Moléculaire et Stratégies Théranostiques (IMoST), Institut National de la Santé et de la Recherche Médicale (INSERM)-Université Clermont Auvergne (UCA), Interfaces & biosensors - Interfaces & biocapteurs, 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), 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), and Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Chemistry, [SDV]Life Sciences [q-bio], Two step, Cancer therapy, Nanoparticle, Nanotechnology, 02 engineering and technology, General Chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, 0104 chemical sciences, Nanomedicine, Click chemistry, Nanoparticles, [CHIM]Chemical Sciences, Click Chemistry, Bioorthogonal chemistry, 0210 nano-technology
Abstract: International audience; Over the years, click and bioorthogonal reactions have been the subject of considerable research efforts. These high-performance chemical reactions have been developed to meet requirements not often provided by the chemical reactions commonly used today in the biological environment, such as selectivity, rapid reaction rate and biocompatibility. Click and bioorthogonal reactions have been attracting increasing attention in the biomedical field for the engineering of nanomedicines. In this review, we study a compilation of articles from 2014 to the present, using the terms "click chemistry and nanoparticles (NPs)" to highlight the application of this type of chemistry for applications involving NPs intended for biomedical applications. This study identifies the main strategies offered by click and bioorthogonal chemistry, with respect to passive and active targeting, for NP functionalization with specific and multiple properties for imaging and cancer therapy. In the final part, a novel and promising approach for "two step" targeting of NPs, called pretargeting (PT), is also discussed; the principle of this strategy as well as all the studies listed from 2014 to the present are presented in more detail.
Published: 2021
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27. Block Copolymers Based on Ethylene and Methacrylates Using a Combination of Catalytic Chain Transfer Polymerisation (CCTP) and Radical Polymerisation

Author: David M. Haddleton, Franck D'Agosto, Florian Baffie, Georgios Patias, Vincent Monteil, Fabrice Brunel, Lionel Perrin, Ataulla Shegiwal, Ludmilla Verrieux, Catalyse, Polymérisation, Procédés et Matériaux (CP2M), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École supérieure de Chimie Physique Electronique de Lyon (CPE)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie et Biochimie Moléculaires et Supramoléculaires (ICBMS), Université de Lyon-Université de Lyon-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-École Supérieure Chimie Physique Électronique de Lyon-Centre National de la Recherche Scientifique (CNRS), and Centre National de la Recherche Scientifique (CNRS)
Subjects: Ethylene, 010405 organic chemistry, food and beverages, Chain transfer, General Medicine, General Chemistry, 010402 general chemistry, Methacrylate, 01 natural sciences, Catalysis, 0104 chemical sciences, chemistry.chemical_compound, [CHIM.POLY]Chemical Sciences/Polymers, Methacrylic acid, chemistry, Polymerization, Catalytic chain transfer, Polymer chemistry, Copolymer, [CHIM]Chemical Sciences, Methyl methacrylate
Abstract: International audience; Two scalable polymerisation methods are used in combination for the synthesis of ethylene and methacrylate block copolymers. w-Unsaturated methacrylic oligomers (MMA n) produced by catalytic chain transfer (co)polymerisation (CCTP) of methyl methacrylate (MMA) and methacrylic acid (MAA) are used as reagents in the radical polymerisation of ethylene (E) in dimethyl carbonate solvent under relatively mild conditions (80 bar, 70 8C). Kinetic measurements and analyses of the produced copolymers by size exclusion chromatography (SEC) and a combination of nuclear magnetic resonance (NMR) techniques indicate that MMA n is involved in a degradative chain transfer process resulting in the formation of (MMA) n-b-PE block copolymers. Molecular modelling performed by DFT supports the overall reactivity scheme and observed selectivities. The effect of MMA n molar mass and composition is also studied. The block copolymers were characterised by differential scanning calorimetry (DSC) and their bulk behaviour studied by SAXS/WAXS analysis.
Published: 2021
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28. Electrochemical Etching of Germanium in Ionic Liquids without the Use of Toxic and Corrosive Reagents

Author: Mikhail P. Egorov, Anna Ya. Kozmenkova, Viatcheslav Jouikov, Alexey S. Galushko, Mikhail A. Syroeshkin, Sofia D. Farafonova, Evgeniya A. Saverina, Valentine P. Ananikov, ND Zelinsky Institute of Organic Chemistry [Moscow, Russia], Mendeleev University of Chemical Technology of Russia, Nansen International Environmental and Remote Sensing Center - Russia (NIIERSC), 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), RFBR Russian Foundation for Basic Research (RFBR), Moscow City Government [21-33-70070], 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: Materials science, Energy Engineering and Power Technology, chemistry.chemical_element, Germanium, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, ionic liquids, Biomaterials, chemistry.chemical_compound, Materials Chemistry, [CHIM]Chemical Sciences, Electrochemical etching, Renewable Energy, Sustainability and the Environment, electrochemical etching, 021001 nanoscience & nanotechnology, 0104 chemical sciences, germanium, environmental compatibility, Chemical engineering, chemistry, Reagent, Ionic liquid, 0210 nano-technology, Porous medium, porous materials
Abstract: International audience; For the first time, the possibility of obtaining porous germanium from both single-crystal and polycrystalline starting materials using environmentally friendly (in contrast to the commonly used HF and HCl) imidazolium ionic liquids (IL) was shown. It was demonstrated that pore formation depended significantly on the viscosity of the IL, on the etching current density and etching time, and on defects and imperfections of the substrate surface. By varying these parameters, the rates of two competing processes - formation and growth of pores and electropolishing - could be adjusted, consequently allowing germanium with a various structured surface, including a porous surface. In particular, using a more viscous IL (for example, [BMIM][PF6] versus [BMIM][BF4]) made it possible to reduce the rate of dissolution of the germanium dioxide surface layer; as a result, the formation and growth of pores became a dominant process. At the same time, the dissolution rate of the already formed porous layer (electropolishing) increased with the etching current density and the number of defects and imperfections of the germanium surface.
Published: 2021
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29. Impact of the Difluoromethylene Group in the Organocatalyzed Acylative Kinetic Resolution of α,α‐Difluorohydrins

Author: Adrien Quintard, Daniela Andrei, Jean-Marc Pons, Jérémy Merad, Maurice Médebielle, Cyril Bressy, Titouan Desrues, Jean-Luc Parrain, 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 et Biochimie Moléculaires et Supramoléculaires (ICBMS), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-École Supérieure Chimie Physique Électronique de Lyon-Centre National de la Recherche Scientifique (CNRS), ANR-18-CE07-0036,AMPLI,Amplification d'Enantiosélectivité en Organocatalyse: Criblage Rapide de Catalyseurs, Développements & Applications Synthétiques(2018), Université de Lyon-Université de Lyon-École Supérieure de Chimie Physique Électronique de Lyon (CPE)-Institut National des Sciences Appliquées de Lyon (INSA Lyon), and Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Enantioselective, Kinetic Resolution, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Organcatalysis, Enantioselective synthesis, chemistry.chemical_element, Context (language use), General Medicine, General Chemistry, 010402 general chemistry, 01 natural sciences, Combinatorial chemistry, Catalysis, 0104 chemical sciences, Adduct, Kinetic resolution, Acylation, chemistry, Alcohols, fluorine, Organocatalysis, Fluorine, Moiety
Abstract: International audience; Due to the omnipresence of chiral organofluorine compounds in pharmaceutical, agrochemical, and material chemistry, the development of enantioselective methods for their preparation is highly desirable. In the present study, the enantioselective organocatalyzed acylation of a,a-difluorohydrins using a commercially available chiral isothiourea is reported through a kinetic resolution (KR) process. It reveals that the difluoromethylene moiety (C(sp 3)F 2) can serve as a directing group through electrostatic fluorine-cation interactions, greatly improving the enantioselectivity of the KR. In this context, a broad range of fluorinated alcohols such as valuable 4,4-difluoro-1,3-diols could be synthesized with exquisite enantiocontrol (typically > 99:1 er). Turning to 2,2difluoro-1,3-diols, we also demonstrated that aromatic and fluorinated groups were mutually compatible to provide the expected enantioenriched adducts with > 99:1 er.
Published: 2021
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30. Uranyl(VI) Triflate as Catalyst for the Meerwein–Ponndorf–Verley Reaction

Author: Louis Monsigny, Thibault Cantat, Jean-Claude Berthet, Marie Kobylarski, Pierre Thuéry, 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-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Fondation Louis D.−Institut de France, European Project: ERC CoG n°818260 ,ReNewHydrides, 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), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Catalytic transformation, 010405 organic chemistry, Chemistry, chemistry.chemical_element, [CHIM.CATA]Chemical Sciences/Catalysis, Uranium, 010402 general chemistry, Uranyl, 01 natural sciences, Medicinal chemistry, 0104 chemical sciences, Catalysis, Inorganic Chemistry, Solvent, chemistry.chemical_compound, Oxophilicity, Hemiacetal, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Physical and Theoretical Chemistry, Trifluoromethanesulfonate
Abstract: International audience; Catalytic transformation of oxygenated compounds is challenging in f-element chemistry due to the high oxophilicity of the f-block metals. We report here the first Meerwein–Ponndorf–Verley (MPV) reduction of carbonyl substrates with uranium-based catalysts, in particular from a series of uranyl(VI) compounds where [UO2(OTf)2] (1) displays the greatest efficiency (OTf = trifluoromethanesulfonate). [UO2(OTf)2] reduces a series of aromatic and aliphatic aldehydes and ketones into their corresponding alcohols with moderate to excellent yields, using iPrOH as a solvent and a reductant. The reaction proceeds under mild conditions (80 °C) with an optimized catalytic charge of 2.3 mol % and KOiPr as a cocatalyst. The reduction of aldehydes (1–10 h) is faster than that of ketones (>15 h). NMR investigations clearly evidence the formation of hemiacetal intermediates with aldehydes, while they are not formed with ketones.
Published: 2021
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31. Extraction of Crude Oil Endogenous Surfactants by an Optimum Three-Phase Microemulsion System: Relation between Interfacial Behavior and a Molecular Fingerprint Obtained by Ultrahigh-Resolution Mass Spectrometry

Author: Leticia M. Ligiero, Valérie Molinier, Julien Maillard, Jean-Marie Aubry, Carlos Afonso, Matthieu Loriau, Jesús F. Ontiveros, Charlotte Mase, Johann Le Maître, Pierre Giusti, Guillaume Lemahieu, 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), Pôle d'Etude et de Recherche de Lacq [Total] (PERL), Centre Européen de Recherches et Techniques TOTAL, TOTAL FINA ELF, Chimie Organique et Bioorganique : Réactivité et Analyse (COBRA), Institut de Chimie Organique Fine (IRCOF), Université de Rouen Normandie (UNIROUEN), 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)-Centre National de la Recherche Scientifique (CNRS)-Université de Rouen Normandie (UNIROUEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), and Centre scientifique et Technique Jean Feger (CSTJF)
Subjects: Materials science, Chromatography, [CHIM.ORGA]Chemical Sciences/Organic chemistry, General Chemical Engineering, Extraction (chemistry), Energy Engineering and Power Technology, Endogenous Surfactants, Extraction, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, Molecular Fingerprint, Crude oil, Mass spectrometry, Lipids, 01 natural sciences, 0104 chemical sciences, Petrochemicals, Fuel Technology, Three-phase, Ultrahigh resolution, Emulsions, Microemulsion, 0210 nano-technology, Materials
Abstract: International audience; A novel method is described to extract crude oil surface active species. It is based on the formation of balanced three-phase microemulsions (optimum Winsor III systems) with a well-defined temperature-sensitive nonionic surfactant. The crude oil surface-active species are concentrated in the middle-phase microemulsion, which is separated. The interfacial material is then recovered in the surfactant-rich aqueous phase after cooling. This method was applied to five crude oils and the interfacial materials were then analyzed by Fourier transform ion cyclotron resonance mass spectroscopy (FT-ICR MS). This novel extraction method compares well with the established “wet-silica” method, as evidenced by the analysis in the negative electrospray ESI(−) mode of the interfacial materials of the same crude extracted by the two methods. The analytical data have been related to the interfacial activity of the crude oils, namely, their tendency to form stable emulsions with water or viscous phases in surfactant/oil/water systems at equilibrium, and to their equivalent alkane carbon numbers (EACN). The interfacial materials are confirmed to be responsible for the increased stability of water-in-oil emulsions.
Published: 2021
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32. Investigation of aluminum phthalocyanine chloride as acceptor material in planar organic solar cells: comparative study with fullerene

Author: J.C. Bernède, Hind Lamkaouane, Guy Louarn, Linda Cattin, Mustapha Diani, Mohammed Addou, Hajar Ftouhi, Université Abdelmalek Essaâdi (UAE), Institut des Matériaux Jean Rouxel (IMN), Université de Nantes - UFR des Sciences et des Techniques (UN UFR ST), Université de Nantes (UN)-Université de Nantes (UN)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Ecole Polytechnique de l'Université de Nantes (EPUN), Université de Nantes (UN)-Université de Nantes (UN), Université Hassan II [Casablanca] (UH2MC), MOLTECH-Anjou, Université d'Angers (UA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and le Centre National de la Recherche Scientifique et Technique (CNRST) - PPR/2015/9le Partenariat Hubert Curien (PHC) franco-marocain TOUBKAL - 41406ZC
Subjects: Electron mobility, Materials science, Fullerene, Organic solar cell, business.industry, Open-circuit voltage, Energy conversion efficiency, Heterojunction, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, 01 natural sciences, 7. Clean energy, Acceptor, Atomic and Molecular Physics, and Optics, 0104 chemical sciences, Electronic, Optical and Magnetic Materials, Absorbance, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], Optoelectronics, Electrical and Electronic Engineering, 0210 nano-technology, business
Abstract: International audience; Aluminum Phthalocyanine Chloride (AlPcCl) is generally known as donor material in organic photovoltaic cells (OPVs). Nevertheless, in the present study we have demonstrated a successful use of AlPcCl as acceptor material to replace fullerene (C-60) in a planar heterojunction OPVs based Alpha-Sexithiophene (alpha-6T) as donor material. For this purpose, we have elaborated two series of OPVs: alpha-6T/AlPcCl and alpha-6T/C-60 using thermal sublimation technique. After the optimization of the AlPcCl thickness we have compared both solar cells current density vs. voltage characteristics, we have shown that the use of AlPcCl as acceptor instead of C-60 induces to an increase in the open circuit voltage (V-oc) and the short current density (J(sc)) values by 18% and 23%, respectively, from 0.5 to 0.61 V and from 6.10 to 7.98 mA/cm(2), while, we have obtained a decrease in the shunt resistance which has dropped the fill factor (FF) from 58 to 51%. The V-oc and J(sc) increase allows to increase the power conversion efficiency by 28%. These findings have been supported by absorbance measurements and morphological studies. The V-oc and J(sc) increase have been discussed and assigned to the difference between the theoretical V-oc of both heterojunctions, and to the complimentary absorption of AlPcCl with alpha-6T. While, the FF deceases has been attributed to the low electron mobility of AlPcCl compared with C-60. These findings, brought in the spotlight the potential of the metal phthalocyanines, which can open up a wide range of possibilities to test other materials based like this family.
Published: 2021
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33. Electrochemical Strain Dynamics in Noble Metal Nanocatalysts

Author: Guillaume Braesch, H. Isern, Isaac Martens, Florian Russello, Jakub Drnec, Michal Ronovsky, Veijo Honkimäki, Marta Mirolo, Eric Sibert, Elisabeth Hornberger, Marian Chatenet, Raphaël Chattot, Peter Strasser, European Synchroton Radiation Facility [Grenoble] (ESRF), Electrochimie Interfaciale et Procédés (EIP), Laboratoire d'Electrochimie et de Physico-chimie des Matériaux et des Interfaces (LEPMI), Institut de Chimie du CNRS (INC)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA), and Technische Universität Berlin (TU)
Subjects: Chemistry, Nanotechnology, [CHIM.CATA]Chemical Sciences/Catalysis, 02 engineering and technology, General Chemistry, engineering.material, 010402 general chemistry, 021001 nanoscience & nanotechnology, Electrochemistry, 01 natural sciences, 7. Clean energy, Biochemistry, Catalysis, Nanomaterial-based catalyst, 0104 chemical sciences, Colloid and Surface Chemistry, Adsorption, engineering, Energy transformation, Noble metal, Cyclic voltammetry, 0210 nano-technology, Absorption (electromagnetic radiation), ComputingMilieux_MISCELLANEOUS
Abstract: The theoretical design of effective metal electrocatalysts for energy conversion and storage devices relies greatly on supposed unilateral effects of catalysts structure on electrocatalyzed reactions. Here, by using high-energy X-ray diffraction from the new Extremely Brilliant Source of the European Synchrotron Radiation Facility (ESRF-EBS) on device-relevant Pd and Pt nanocatalysts during cyclic voltammetry experiments in liquid electrolytes, we reveal the near ubiquitous feedback from various electrochemical processes on nanocatalyst strain. Beyond challenging and extending the current understanding of practical nanocatalysts behavior in electrochemical environment, the reported electrochemical strain provides experimental access to nanocatalysts absorption and adsorption trends (i.e., reactivity and stability descriptors) operando. The ease and power in monitoring such key catalyst properties at new and future beamlines is foreseen to provide a discovery platform toward the study of nanocatalysts encompassing a large variety of applications, from model environments to the device level.
Published: 2021
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34. Magnetic Hysteresis in a Monolayer of Oriented 6 nm CsNiCr Prussian Blue Analogue Nanocrystals

Author: Christophe Cartier dit Moulin, M.-A. Arrio, Laurent Lisnard, Edwige Otero, Weibin Li, Sandra Mazerat, Philippe Ohresser, Laure Catala, Luqiong Zhang, Philippe Sainctavit, Talal Mallah, Synchrotron SOLEIL (SSOLEIL), Centre National de la Recherche Scientifique (CNRS), Institut Parisien de Chimie Moléculaire (IPCM), Chimie Moléculaire de Paris Centre (FR 2769), Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie Moléculaire et des Matériaux d'Orsay (ICMMO), Institut de Chimie du CNRS (INC)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), Institut de minéralogie, de physique des matériaux et de cosmochimie (IMPMC), and Muséum national d'Histoire naturelle (MNHN)-Institut de recherche pour le développement [IRD] : UR206-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Prussian blue, Coordination sphere, Magnetic circular dichroism, 02 engineering and technology, Coercivity, 010402 general chemistry, 021001 nanoscience & nanotechnology, Linear dichroism, Magnetic hysteresis, 01 natural sciences, 0104 chemical sciences, Inorganic Chemistry, Condensed Matter::Materials Science, Magnetization, chemistry.chemical_compound, Crystallography, chemistry, Monolayer, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, 0210 nano-technology, ComputingMilieux_MISCELLANEOUS
Abstract: Prussian blue analogue nanocrystals of the CsINiII[CrIII(CN)6] cubic network with 6 nm size were assembled as a single monolayer on highly organized pyrolytic graphite (HOPG). X-ray magnetic circular dichroism (XMCD) studies, at the Ni and Cr L2,3 edges, reveal the presence of an easy plane of magnetization evidenced by an opening of the magnetic hysteresis loop (coercive field of ≈200 Oe) when the magnetic field, B, is at 60° relative to the normal to the substrate. The angular dependence of the X-ray natural linear dichroism (XNLD) reveals both an orientation of the nanocrystals on the substrate and an anisotropy of the electronic cloud of the NiII and CrIII coordination sphere species belonging to the nanocrystals' surface. Ligand field multiplet (LFM) calculations that reproduce the experimental data are consistent with an elongated tetragonal distortion of surface NiII coordination sphere responsible for the magnetic behavior of monolayer.
Published: 2021
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35. Local Structure and Magnetism of La1–xMxPO4 (M = Sm, 239Pu, 241Am) Explained by Experimental and Computational Analyses

Author: Md. Ashraful Islam, Eric Colineau, Hélène Bolvin, Karin Popa, Laura Martel, Jean-Christophe Griveau, Jean-François Vigier, European Commission - Joint Research Centre [Karlsruhe] (JRC), Systèmes étendus et magnétisme (LCPQ) (SEM), Laboratoire de Chimie et Physique Quantiques Laboratoire (LCPQ), 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)-Fédération de recherche « Matière et interactions » (FeRMI), 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)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS), ANR-17-CE06-0010,ACTIpNMR,déplacements de RMN paramagnétiques pour les actinides : au délà du modèle des lanthanides(2017), Laboratoire de Chimie et Physique Quantiques (LCPQ), Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), and Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)
Subjects: Materials science, Condensed matter physics, Magnetism, 02 engineering and technology, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Local structure, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, General Energy, Physical and Theoretical Chemistry, 0210 nano-technology
Abstract: International audience; With their high chemical and self-irradiation stability, crystalline monazites are among the most promising materials for the encapsulation of nuclear wastes. Yet, the local and magnetic structures of the matrices doped with low-content actinide cation, depicted as most resistant, are still unclear. This limits the development of theoretical approaches predicting their behavior under extreme conditions—self-irradiation and long-term leaching. Here, we characterize the model matrices La1–xMxPO4 (0 ≤ x ≤ 0.10)—with M = Sm, 239Pu, 241Am—by X-ray diffraction and solid-state 31P NMR. As an example, we confirm that La0.96241Am0.04PO4 has higher self-irradiation resistance compared to 241AmPO4. Further, computational analyses show that magnetic properties of the Pu complex are strongly affected by the J-mixing and the paramagnetic NMR shifts are dominated by the Fermi contact contribution, arising from delocalization of the spin density of the cation toward the phosphorus through the bonds.
Published: 2021
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36. Continuous flow synthesis of Celecoxib from 2-bromo-3,3,3-trifluoropropene

Author: Philippe Jubault, Julien Legros, Thomas Poisson, Maria V. Ivanova, 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), 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: active pharmaceutical ingredients, Green chemistry, organolithium chemistry, Ketone, oxidation, Alcohol, 010402 general chemistry, 01 natural sciences, Aldehyde, chemistry.chemical_compound, organofluorine chemistry, [CHIM]Chemical Sciences, Fluid Flow and Transfer Processes, chemistry.chemical_classification, Trifluoromethyl, 010405 organic chemistry, Organic Chemistry, Regioselectivity, Organofluorine chemistry, Combinatorial chemistry, Communications, NSAID, 3. Good health, 0104 chemical sciences, chemistry, Chemistry (miscellaneous), Yield (chemistry)
Abstract: Graphical abstract We describe the total flow synthesis of the widely prescribed anti-inflammatory COX-2 inhibitor Celecoxib from 2-bromo-3,3,3-trifluoropropene, as a convenient and available trifluoromethyl building block, to generate trifluoropropynyl lithium and to trap it immediately with an aldehyde. Oxidation of the obtained alcohol into ketone followed by condensation with 4-sulfamidophenylhydrazine afforded the targeted drug with full regioselectivity. It is noteworthy that the quality of these flow reactions (50% overall yield within 1 h cumulated residence time over 3 steps) directly furnished the target API and intermediates with excellent purity. Supplementary Information The online version contains supplementary material available at 10.1007/s41981-021-00205-x.
Published: 2021
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37. Trinuclear Cyanido‐Bridged [Cr 2 Fe] Complexes: To Be or not to Be a Single‐Molecule Magnet, a Matter of Straightness

Author: Jean-Pascal Sutter, Céline Pichon, Carine Duhayon, Nathalie Guihéry, Valentin Jubault, Nicolas Suaud, 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), Systèmes étendus et magnétisme (LCPQ) (SEM), Laboratoire de Chimie et Physique Quantiques Laboratoire (LCPQ), 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)-Fédération de recherche « Matière et interactions » (FeRMI), 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)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS), ANR-17-CE07-0007,AnisoChirMag,Anisotropie Optique au sein d'Aimants Moléculaires Chiraux: Vers une Lecture Optique de l'Orientation du Spin(2017), 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), Laboratoire de Chimie et Physique Quantiques (LCPQ), Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), and Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)
Subjects: Steric effects, 010405 organic chemistry, Chemistry, Magnetism, Organic Chemistry, Relaxation (NMR), General Chemistry, 010402 general chemistry, 01 natural sciences, Catalysis, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Magnetization, Crystallography, Magnetic anisotropy, Pentagonal bipyramidal molecular geometry, Single-molecule magnets, Anisotropy, Moiety, Single-molecule magnet, Ab initio calculations, Pentagonal bipyramid
Abstract: International audience; Trinuclear systems of formula [{Cr(LN3O2Ph)(CN)2}2M(H2LN3O2R)] (M=MnII and FeII, LN3O2R stands for pentadentate ligands) were prepared in order to assess the influence of the bending of the apical M−N≡C linkages on the magnetic anisotropy of the FeII derivatives and in turn on their Single-Molecule Magnet (SMM) behaviors. The cyanido-bridged [Cr2M] derivatives were obtained by assembling trans-dicyanido CrIII complex [Cr(LN3O2Ph)(CN)2]− and divalent pentagonal bipyramid complexes [MII(H2LN3O2R)]2+ with various R substituents (R=NH2, cyclohexyl, S,S-mandelic) imparting different steric demand to the central moiety of the complexes. A comparative examination of the structural and magnetic properties showed an obvious effect of the deviation from straightness of the M−N≡C alignment on the slow relaxation of the magnetization exhibited by the [Cr2Fe] complexes. Theoretical calculations have highlighted important effects of the bending of the apical C−N−Fe linkages on both the magnetic anisotropy of the FeII center and the exchange interactions with the CrIII units.
Published: 2021
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38. Synthesis, Structural Characterization and Antiproliferative Activity of Gold(I) and Gold(III) Complexes Bearing Thioether‐Functionalized N‐Heterocyclic Carbenes

Author: Riccardo De Marco, Marco Dal Grande, Marco Baron, Laura Orian, Claudia Graiff, Thierry Achard, Stéphane Bellemin‐Laponnaz, Alexander Pöthig, Cristina Tubaro, Universita degli Studi di Padova, Institut de Physique et Chimie des Matériaux de Strasbourg (IPCMS), Université de Strasbourg (UNISTRA)-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, 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), University of Parma = Università degli studi di Parma [Parme, Italie], Technische Universität Munchen - Université Technique de Munich [Munich, Allemagne] (TUM), Technische Universität München [München] (TUM), Università degli Studi di Padova = University of Padua (Unipd), Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), Università degli studi di Parma = University of Parma (UNIPR), and Bellemin-Laponnaz, Stéphane
Subjects: Inorganic Chemistry, 010405 organic chemistry, [CHIM] Chemical Sciences, [CHIM]Chemical Sciences, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences
Abstract: International audience; A series of gold(I) and gold(III) complexes with N-heterocyclic carbene ligands functionalized with a pendant thioether group (NHC-SR) was synthesized with straightforward procedures and characterized in solution with NMR spectroscopy and ESI-MS spectrometry, as well as in the solid state by means of single crystal X-ray diffraction analysis. Selected experimental aspects were rationalized through relativistic DFT calculations. The gold(I) and gold(III) complexes displayed moderate in vitro cytotoxicity towards breast cancer cells MCF7.
Published: 2021
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39. New insights into lignin electrolysis on nickel-based electrocatalysts: Electrochemical performances before and after oxygen evolution

Author: N. Grimaldos-Osorio, K. Beliaeva, Philippe Vernoux, Laurence Burel, A. Caravaca, E. Ruiz-López, 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), Universidad de Castilla-La Mancha (UCLM), and IRCELYON-Microscopie (MICROSCOPIE)
Subjects: hydrogen production, Energy Engineering and Power Technology, 02 engineering and technology, 010402 general chemistry, Electrochemistry, 7. Clean energy, 01 natural sciences, Catalysis, law.invention, chemistry.chemical_compound, Catalytic reforming, law, Ni-based electrocatalyst, Molecule, Lignin, Electrolysis, β-O-4 linkage model, Electrolysis of water, Renewable Energy, Sustainability and the Environment, Chemistry, Oxygen evolution, [CHIM.CATA]Chemical Sciences/Catalysis, 021001 nanoscience & nanotechnology, Condensed Matter Physics, 0104 chemical sciences, [CHIM.POLY]Chemical Sciences/Polymers, Fuel Technology, Lignin electrolysis, Chemical engineering, [CHIM.OTHE]Chemical Sciences/Other, 0210 nano-technology
Abstract: International audience; The production of H2 via electrolysis seems to be the best alternative to traditional catalytic reforming processes. The electrolysis of lignin allows to produce pure H2 while valorizing a low-price biomass waste with (theoretically) lower energy requirements than water electrolysis. Previous studies were published in the last years dealing with the electro-oxidation of lignin on Ni-based catalysts. Ni is a robust non-expensive metal that presents a wide variety of oxidation states and phase transitions. To this date, it is still not completely clear how these states/transitions activate the lignin molecule. The aim of this study is to get more insights into the cleavage of the main chemical bonds present in the complex lignin structure over different Ni oxidation states. A Ni/C catalyst, prepared by the polyol method, was thoroughly characterized and tested for the electro-oxidation of both, lignin and 2-phenoxyethanol, where the latter is a model molecule representative of the quintessential β-O-4 linkage in lignin.
Published: 2021
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40. Absolute configuration of a [1]rotaxane determined from vibrational and electronic circular dichroism spectra

Author: Isabelle Opalinski, Sébastien Papot, Prasad L. Polavarapu, Grégory Pieters, Andrew R. Puente, Noël Pairault, Jeanne Crassous, Adrien Bessaguet, Vanderbilt University [Nashville], Institut de Chimie des Milieux et Matériaux de Poitiers (IC2MP), Université de Poitiers-Institut national des sciences de l'Univers (INSU - CNRS)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Médicaments et Technologies pour la Santé (MTS), Université Paris-Saclay-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)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), 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), 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: Circular dichroism, Rotaxane, 010402 general chemistry, electronic circular dichroism, 01 natural sciences, Catalysis, Spectral line, Analytical Chemistry, Drug Discovery, [CHIM]Chemical Sciences, density functional theory, Spectroscopy, Pharmacology, 010405 organic chemistry, Chemistry, Organic Chemistry, Absolute configuration, Diastereomer, vibrational circular dichroism, mechanical planar chirality, 3. Good health, 0104 chemical sciences, absolute configuration, Crystallography, Vibrational circular dichroism, Density functional theory, Enantiomer
Abstract: International audience; The experimental vibrational circular dichroism (VCD) and electronic circular dichroism (ECD) spectra were measured for the enantiomers of [1]rotaxane 1. These experimental spectra have been analyzed using predicted VCD and ECD spectra for (S, Rmp) or (S, Smp) diastereomers using density functional theory. This comparison allowed for a definitive assignment of the absolute configuration of 1.
Published: 2021
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41. Precise Rate Control of Pseudorotaxane Dethreading by pH-Responsive Selectively Functionalized Cyclodextrins

Author: Matthieu Sollogoub, Sawsen Cherraben, Guillaume Vives, Jérémy Scelle, Bernold Hasenknopf, Institut Parisien de Chimie Moléculaire (IPCM), Chimie Moléculaire de Paris Centre (FR 2769), Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), and Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)
Subjects: [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Chemistry, Organic Chemistry, Substitution (logic), Rate control, Stimulus (physiology), 010402 general chemistry, 01 natural sciences, Biochemistry, Combinatorial chemistry, 0104 chemical sciences, 3. Good health, Threading (manufacturing), Physical and Theoretical Chemistry
Abstract: International audience; A family of cyclodextrins functionalized with zero, one, two, or six amines was shown to control the rate of their threading and dethreading on a molecular axle depending on the pH and their substitution pattern. The originality of this system lies in the rate control of the switch by operating the stimulus directly on the macrocycle.
Published: 2021
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42. Doxorubicin‐Sensitized Luminescence of NIR‐Emitting Ytterbium Liposomes: Towards Direct Monitoring of Drug Release

Author: Sara Lacerda, Éva Tóth, Frédéric Szeremeta, Sandra Même, Anthony Delalande, Célia S. Bonnet, Stéphane Petoud, Agnès Pallier, Chantal Pichon, Svetlana V. Eliseeva, Centre de biophysique moléculaire (CBM), Université d'Orléans (UO)-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 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 Frapart, Isabelle
Subjects: Ytterbium, Luminescence, Materials science, Infrared Rays, [SDV]Life Sciences [q-bio], chemistry.chemical_element, Breast Neoplasms, 02 engineering and technology, 010402 general chemistry, Photochemistry, 01 natural sciences, Catalysis, Polyethylene Glycols, Mice, Cell Line, Tumor, medicine, Animals, Chelation, Doxorubicin, Liposome, Antibiotics, Antineoplastic, Molecular Structure, General Medicine, General Chemistry, 021001 nanoscience & nanotechnology, Magnetic Resonance Imaging, 3. Good health, 0104 chemical sciences, [SDV] Life Sciences [q-bio], Drug Liberation, chemistry, Liposomes, Drug delivery, Nanomedicine, Female, 0210 nano-technology, Preclinical imaging, medicine.drug
Abstract: International audience; Drug-loaded liposomes are typical examples of nanomedicine. We show here that doxorubicin, the anti-cancer agent in the liposomal drug Doxil ® , can sensitize Ytterbium (Yb 3+ ) and generate its near infrared (NIR) emission. When doxorubicin and amphiphilic Yb 3+ chelates are incorporated into liposomes, the sensitized emission of Yb 3+ is dependent on the integrity of the particles which can be used to monitor drug release. We also established the first demonstration that the NIR Yb 3+ emission signal is observable in living mice following intratumoral injection of the Yb 3+ -doxorubicin-liposomes, using a commercial macroscopic setup equipped with a near-infrared camera.
Published: 2021
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43. Subsurface‐Carbon‐Induced Local Charge of Copper for an On‐Surface Displacement Reaction

Author: Ye Sun, Flemming Besenbacher, Cristina Mattioli, Wenlong E, Shaoshan Wang, Miao Yu, Lev Kantorovich, André Gourdon, Xueming Yang, Pengcheng Ding, Zhuo Li, Groupe NanoSciences (CEMES-GNS), Centre d'élaboration de matériaux et d'études structurales (CEMES), Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie de Toulouse (ICT-FR 2599), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Toulouse III - Paul Sabatier (UT3), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA), Harbin Institute of Technology (HIT), Dalian Institute of Chemical Physics (DICP), Chinese Academy of Sciences [Changchun Branch] (CAS), Center for Condensed Matter Science and Technology, 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)-Centre National de la Recherche Scientifique (CNRS), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Department of Physics, King's College London, Interdisciplinary Nanoscience Center (iNANO), and Aarhus University [Aarhus]
Subjects: Materials science, Proton, FOS: Physical sciences, chemistry.chemical_element, 010402 general chemistry, 01 natural sciences, Catalysis, Carbide, Deprotonation, Physics - Chemical Physics, Atom, displacement reaction, on-surface synthesis, Single displacement reaction, Chemical Physics (physics.chem-ph), catalysis, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, General Chemistry, Copper, displacement reactions, 0104 chemical sciences, Condensed Matter - Other Condensed Matter, Carbon doping, local charge, chemistry, [PHYS.COND.CM-GEN]Physics [physics]/Condensed Matter [cond-mat]/Other [cond-mat.other], Physical chemistry, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], Carbon, Other Condensed Matter (cond-mat.other), carbon doping
Abstract: Transition metal carbides have sparked unprecedented enthusiasm as high-performance catalysts in recent years. Still, the catalytic properties of copper (Cu) carbide remain unexplored. By introducing subsurface carbon (C) to Cu(111), displacement reaction of proton in carboxyl acid group with single Cu atom is demonstrated at the atomic scale and room temperature. Its occurrence is attributed to the C-doping induced local charge of surface Cu atoms (up to +0.30 e/atom), which accelerates the rate of on-surface deprotonation via reduction of the corresponding energy barrier, thus enabling the instant displacement of a proton with a Cu atom when the molecules land on the surface. Such well-defined and robust Cu$^{\delta +}$ surface based on the subsurface C doping offers a novel catalytic platform for on-surface synthesis., Comment: Angewandte Chemie International Edition, Wiley-VCH Verlag, 2021
Published: 2021
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44. Bottom-Up Design of Configurable Oligomer-Derived Conducting Metallopolymers for High-Power Electrochemical Energy Storage

Author: Evgeniya Vorobyeva, Mathieu Salanne, Maria R. Lukatskaya, Franziska Lissel, Eidgenössische Technische Hochschule - Swiss Federal Institute of Technology [Zürich] (ETH Zürich), Leibniz-Institut für Polymerforschung Dresden e.V. (IPF), Leibniz Association, Technische Universität Dresden = Dresden University of Technology (TU Dresden), 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), PHysicochimie des Electrolytes et Nanosystèmes InterfaciauX (PHENIX), Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-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 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 ), and Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)
Subjects: Battery (electricity), Materials science, Metal ions in aqueous solution, Supramolecular chemistry, General Physics and Astronomy, chemistry.chemical_element, Nanotechnology, 02 engineering and technology, 010402 general chemistry, 7. Clean energy, 01 natural sciences, Oligomer, Metal, [SPI]Engineering Sciences [physics], chemistry.chemical_compound, conjugated oligomers, Side chain, General Materials Science, Electrical conductor, supercapacitors, electrochemical energy storage, General Engineering, 021001 nanoscience & nanotechnology, conductive metallopolymers, 0104 chemical sciences, chemistry, visual_art, visual_art.visual_art_medium, Lithium, 0210 nano-technology
Abstract: International audience; In this Perspective, we sketch out a vision of fast charging and self-healable energy systems that are primarily organic, feature only abundant elements, and operate with ions other than lithium. Using conductive oligomers as highly configurable building blocks, it is possible to create intrinsically adaptable conductive polymeric networks that can be rejuvenated and recycled using simple and safe chemical treatments. Using the versatile organic chemistry toolbox, these oligomers can be further functionalized, for example, with redox-active side chains for high charge storage capacity and ligands capable of complexing metal centers. Cross-linking with metal ions converts the soluble oligomers into insoluble supramolecular networks to yield high-performing electrode materials. The oligomer-based approach can thus provide an exceptional level of control to the design of organic-based battery materials.
Published: 2021
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45. Metal-Catalyzed Metathesis of Fluorinated Alkenes: Still a Current Major Challenge

Author: Xavier Pannecoucke, Augustin Nouaille, Samuel Couve-Bonnaire, Jan Lorkowski, Marc Mauduit, Thomas Poisson, Chimie Organique et Bioorganique : Réactivité et Analyse (COBRA), Institut de Chimie Organique Fine (IRCOF), Université de Rouen Normandie (UNIROUEN), 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)-Centre National de la Recherche Scientifique (CNRS)-Université de Rouen Normandie (UNIROUEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Université Le Havre Normandie (ULH), Normandie Université (NU)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut Universitaire de France (IUF), Ministère de l'Education nationale, de l’Enseignement supérieur et de la Recherche (M.E.N.E.S.R.), Normandie Universite (NU), Region Normandie Region Normandie, Centre National de la Recherche Scientifique (CNRS), Universite de Rouen Normandie (URN), INSA Rouen Normandie, Labex SynOrg [ANR-11-LABX-0029], graduate school for research XLChem [ANR-18-EURE-0020], Innovation Chimie Carnot (I2C), MESRI, CNRS (Programme de Prematuration CNRS 2020), ANR-11-LABX-0029,SYNORG,Synthèse Organique : des molécules au vivant(2011), ANR-18-EURE-0020,XL Chem,XLChem, Synthesizing our future(2018), Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Université Le Havre Normandie (ULH), 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), 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), 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), ANR-18-EURE-0020,XL Chem,XLChem, and Synthesizing our future(2018)
Subjects: 010405 organic chemistry, Chemistry, fluoroalkenes, General Chemistry, 010402 general chemistry, Metathesis, 01 natural sciences, Combinatorial chemistry, fluorine chemistry, Catalysis, 0104 chemical sciences, Metal, molybdenum, visual_art, visual_art.visual_art_medium, olefin metathesis, [CHIM]Chemical Sciences, Current (fluid), ruthenium
Abstract: International audience; Whereas the olefin metathesis is recognized as a powerful tool to produce alkene, the use of fluoroalkenes in metathesis-catalyzed reactions still remains a major current challenge. Herein, we presented the main developments in that field both in ring-closing metathesis and cross-metathesis, highlighting the major improvements of these past years.
Published: 2021
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46. Effect of Sodium Concentration on the Synthesis of Faujasite by Two-step Synthesis Procedure

Author: Chunzheng Wang, Svetlana Mintova, Hailing Guo, Lei Zhao, Lijuan Wang, Ge Yang, Institut d'Électronique et des Technologies du numéRique (IETR), Université de Nantes (UN)-Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-CentraleSupélec-Centre National de la Recherche Scientifique (CNRS), China University of Petroleum, School of Mathematics and Statistics [Wuhan], Wuhan University [China], Laboratoire catalyse et spectrochimie (LCS), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Nantes (UN)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-CentraleSupélec-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Université de Caen Normandie (UNICAEN), Normandie Université (NU), and Nantes Université (NU)-Université de Rennes 1 (UR1)
Subjects: Materials science, synthesis, Sodium, chemistry.chemical_element, 02 engineering and technology, engineering.material, 010402 general chemistry, 01 natural sciences, law.invention, chemistry.chemical_compound, Aluminosilicate, law, morphology, [CHIM]Chemical Sciences, zeolite, alkali metal, Crystallization, Zeolite, General Chemistry, Faujasite, 021001 nanoscience & nanotechnology, Alkali metal, 0104 chemical sciences, Amorphous solid, chemistry, Sodium hydroxide, engineering, 0210 nano-technology, Nuclear chemistry
Abstract: International audience; The relationship between concentration of sodium cations and the properties of faujasite (FAU) zeolite using a two-step synthesis procedure including (1) formation of amorphous aluminosilicate precursors and separation of amorphous nanoparticles, and (2) transformation of these amorphous particles into zeolite crystals by treatment with alkali solutions (NaOH) were studied. Three representative samples including two nano-sized zeolites and one micron-sized zeolite were prepared using different concentration of sodium hydroxide. The crystallization process of these zeolites was studied in details by FTIR, NMR, XRD, SEM, TEM, N 2 adsorption. The results indicated that minor changes in the concertation of inorganic cations can significantly shorten the induction period and crystallization time and thus affect the morphology, size and chemical composition of the zeolite crystals.
Published: 2021
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47. Synthesis, characterization, and computational survey of a novel material template o-xylylenediamine

Author: Noureddine Issaoui, Thierry Roisnel, Meriam Tahenti, Houda Marouani, Université de Carthage - University of Carthage, Université de Monastir - University of Monastir (UM), 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: Materials science, Aqueous solution, 010405 organic chemistry, Hydrogen bond, RDG, General Chemistry, 010402 general chemistry, DFT, 01 natural sciences, X-ray diffraction, 0104 chemical sciences, Crystal, Crystallography, X-ray crystallography, [CHIM]Chemical Sciences, Molecule, Density functional theory, Orthorhombic crystal system, Spectroscopy, Photoluminescence, Hirshfeld Surface
Abstract: International audience; A new salt Bis(o-xylylenediammonium) tetrachloride monohydrate, denoted by OXDACl, produces a novel organic-inorganic compound with centrosymmetric property, prepared by slow evaporation technique in an aqueous solution. This one has been assumed a pattern in the orthorhombic Pnma space group, and the following crystallographic parameters obtained are a = 9.0677(9) angstrom, b = 24.282 (2) angstrom, c = 9.4726 (8) angstrom, V = 2085.7 (3)angstrom(3) and Z = 4, at 150 K. It is investigated by X-ray diffraction, fluorescence, infrared, and UV-visible spectroscopy. The crystal wrap is endorsed by the O-H center dot center dot center dot Cl, N-H center dot center dot center dot Cl hydrogen bond interactions among the organic network and the inorganic one, which stabilize the crystal packing. Besides to get a perception into the attitude of these interconnections, Hirshfeld surfaces analysis have been scrutinized. Computational calculations were performed, employing density functional theory (DFT), and were made by comparison with the experimentally determined structure to examine the molecular structure with geometrical optimization, vibrational, and topological parameters of OXDACl by B3LYP/6-311 + + G(d,p) basis.
Published: 2021
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48. New ternary water-soluble support from self-assembly of β-cyclodextrin-ionic liquid and an anionic polymer for a dialysis device

Author: Asmaa Bouyahya, Didier Le Cerf, Géraldine Gouhier, Mohammed Lahcini, Valérie Mesnage, Carole Karakasyan-Dia, Audrey Favrelle-Huret, Sébastien Balieu, Frédéric Guillen, Berthe-Sandra Sembo-Backonly, Institut de Chimie Organique Fine (IRCOF), Université de Rouen Normandie (UNIROUEN), 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)-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), Institut de Chimie du CNRS (INC)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), 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)-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 Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Normandie Université (NU), Chimie Organique et Bioorganique : Réactivité et Analyse (COBRA), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Université de Rouen Normandie (UNIROUEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Université Cadi Ayyad [Marrakech] (UCA), 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), Synthèse et Physico-Chimie de Molécules d'Intérêt Biologique (SPCMIB), 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), Morphodynamique Continentale et Côtière (M2C), Normandie Université (NU)-Normandie Université (NU)-Institut national des sciences de l'Univers (INSU - CNRS)-Université de Rouen Normandie (UNIROUEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Institut Normand de Chimie Moléculaire Médicinale et Macromoléculaire (INC3M), Université Mohammed VI Polytechnique [Ben Guerir] (UM6P), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and ANR-18-EURE-0020,XL Chem,XLChem, Synthesizing our future(2018)
Subjects: Polymers, Health, Toxicology and Mutagenesis, Supramolecular chemistry, Ionic Liquids, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Styrene, chemistry.chemical_compound, Renal Dialysis, Polymer chemistry, Environmental Chemistry, chemistry.chemical_classification, Cyclodextrins, Cyclodextrin, Chemistry, beta-Cyclodextrins, Water, [CHIM.MATE]Chemical Sciences/Material chemistry, General Medicine, 021001 nanoscience & nanotechnology, Pollution, Polyelectrolyte, 0104 chemical sciences, [CHIM.POLY]Chemical Sciences/Polymers, Anionic addition polymerization, Sulfonate, Ionic liquid, 0210 nano-technology, Hybrid material
Abstract: We developed a new hybrid material resulting from an innovative supramolecular tripartite association between an ionic liquid covalently immobilized on primary β-cyclodextrins rim and an anionic water-soluble polymer. Two hydrophilic ternary complexes based on native and permethylated β-cyclodextrins substituted with an ionic liquid and immobilized on poly(styrene sulfonate) (CD-IL+PSS− and CD(OMe)IL+PSS−) were obtained by simple dialysis with a cyclodextrin maximal grafting rate of 25% and 20% on the polymer, respectively. These polyelectrolytes are based on electrostatic interactions between the opposite charges of the imidazolium cation of the ionic liquid and the poly(styrene sulfonate) anion. The inclusion properties of the free cavities of the cyclodextrins and the synergic effect of the polymeric matrix were studied with three reference guests such as phenolphthalein, p-nitrophenol, and 2-anilinonaphthalene-6-sulfonic acid using UV-visible, fluorescent, and NMR spectroscopies. The support has been applied successfully in dialysis device to extract and concentrated aromatic model molecule. This simple and flexible synthetic strategy opens the way to new hybrid materials useful for fast and low-cost ecofriendly extraction techniques relevant for green analytical chemistry.
Published: 2021
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49. Media‐Driven Pd‐Catalyzed Reaction Cascades with 1,3‐Diynamides Leading Selectively to Either Indoles or Quinolines

Author: Alexander Mamontov, Illia Lenko, Rémi Legay, Bernhard Witulski, Carole Alayrac, Laboratoire de chimie moléculaire et thioorganique (LCMT), Centre National de la Recherche Scientifique (CNRS)-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), and Normandie Université (NU)
Subjects: quinolines, Primary (chemistry), cumulenes, 010405 organic chemistry, Chemistry, Homogeneous catalysis, General Medicine, General Chemistry, indoles, 010402 general chemistry, Tetrabutylammonium fluoride, homogeneous catalysis, 01 natural sciences, Combinatorial chemistry, Catalysis, 0104 chemical sciences, Deuterium, ynamides, [CHIM]Chemical Sciences, Product formation
Abstract: International audience; Divergent Pd-catalyzed reaction cascades with various 1,3-diynamides yielding either 2-amino-3-alkynylindoles or 2-amino-4-alkenylquinolines were established. Omitting or adding TBAF (tetrabutylammonium fluoride) to the reaction of N,N-(2-iodophenyl)(4-toluenesulfonyl)-1,3-diynamides with secondary or primary amines in the presence of KOH in THF and catalytic amounts of Pd(PPh3)4 completely changed the outcome of the reaction. In absence of TBAF, 2-amino-3-alkynylindoles were the sole products, while the presence of TBAF switched the product formation to 2-amino-4-alkenylquinolines. Deuterium labeling proceeded selectively at the C3 and C11 positions of the 2-amino-4-alkenylquinoline products and this suggests the unprecedented formation of [4]cumulenimines from 1,3-diynamides as reactive key intermediates.
Published: 2021
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50. Detection of Isotopic Atropisomerism Based on ortho-H/D Discrimination

Author: Kazuya Saito, Christian Roussel, Osamu Kitagawa, Yuuki Fujimoto, Shota Miwa, Asumi Iida, Elsa Caytan, Shibaura Institute of Technology, Tokyo University of Pharmacy and Life Sciences (TUPLS), 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 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), This work was partially supported by JSPS KAKENHI (C 20K06945)., Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), 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: Atropisomer, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Chemistry, Organic Chemistry, Diastereomer, Optically active, 010402 general chemistry, 01 natural sciences, Biochemistry, Spectral line, 0104 chemical sciences, 3. Good health, Crystallography, Asymmetric carbon, Axial chirality, Physical and Theoretical Chemistry
Abstract: International audience; Racemic and optically active 3-(2-deuteriophenyl)-2-(1-phenylpropan-2-yl)quinazoline-4-thiones were prepared. The nuclear magnetic resonance spectra clearly show that they exist as a 1:1 mixture of diastereomers due to the isotopic atropisomerism based on ortho-H/D discrimination (N-C axial chirality) and a chiral carbon.
Published: 2021
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