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157 results on '"Lise-Marie Chamoreau"'

2. Solvothermal Synthesis, Temperature-Dependent Structural Study, and Magnetic Characterization of a Multipolydentate Oxamate-Based 2D Coordination Network

Author

Ang Li, Lise-Marie Chamoreau, Benoît Baptiste, Ludovic Delbes, Yanling Li, Francesc Lloret, Yves Journaux, Laurent Lisnard, Institut Parisien de Chimie Moléculaire (IPCM), Chimie Moléculaire de Paris Centre (FR 2769), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Equipe de Recherche en Matériaux Moléculaires et Spectroscopies (ERMMES), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Chimie Moléculaire de Paris Centre (FR 2769), 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), Instituto de Ciencia Molecular (ICMol), and Universitat de València (UV)

Subjects
[CHIM]Chemical Sciences, [CHIM.COOR]Chemical Sciences/Coordination chemistry, General Materials Science, General Chemistry, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, Condensed Matter Physics
Abstract

International audience; A multi-polydentate N-substituted oxamate ligand bearing an additional carboxylato group has been successfully reacted in solvothermal conditions to form the 2D coordination network (TMA) 3 [CuMn(paba) 2 (OAc)]•8H 2 O (1). This coordination network displays a brick-wall type morphology with, thanks to the augmented connectivity of the ligand, a lower than usual metal ion nuclearity for the building sub-unit. Temperature-dependent structural studies indicate that the layered structure undergoes dehydration at 90°C and remain stable up to 200°C. Magnetic characterizations show that 1 behaves as a ferrimagnet, with a Curie temperature of 2.8 K.

Published
2022

5. Artificial p–n‐like Junction Based on Pure 2D Organic–Inorganic Halide Perovskite Structure Having Naphthalene Diimide Acceptor Moieties

Author

Zhao Feng, Xuelong Liu, Kentaro Imaoka, Tomohiro Ishii, Ganbaatar Tumen‐Ulzii, Xun Tang, George F. Harrington, Benoît Heinrich, Jean‐Charles Ribierre, Lise‐Marie Chamoreau, Lydia Sosa Vargas, David Kreher, Kenichi Goushi, Toshinori Matsushima, Guijiang Zhou, Fabrice Mathevet, and Chihaya Adachi

Subjects
Atomic and Molecular Physics, and Optics, Electronic, Optical and Magnetic Materials
Published
2023

6. Size-dependent compression of threaded alkyldiphosphate in head to head cyclodextrin [3]pseudorotaxanes

Author

Jérémy Scelle, Hugo Vervoitte, Laurent Bouteiller, Lise-Marie Chamoreau, Matthieu Sollogoub, Guillaume Vives, and Bernold Hasenknopf

Subjects
General Chemistry
Abstract

The encapsulation of guests in a confined space enables unusual conformations and reactivities. In particular, the compression of akyl chains has been obtained by self-assembled molecular capsules but such an effect has not been reported in solution for pseudorotaxane architectures. By exploiting the tendency of cyclodextrin (CD) to form head to head [3]pseudorotaxanes and the hydrogen bonding abilities of phosphate groups, we have studied the effect of the CD dimer cavity on the conformation of threaded α,ω-alkyl-diphosphate axles. The formation of [2]pseudorotaxanes and [3]pseudorotaxanes was investigated by a combination of NMR, ITC and X-ray diffraction techniques. In the solid state, the [3]pseudorotaxane with a C

Published
2022

7. Thermally-Induced Spin Crossover and LIESST Effect in the Neutral [FeII(Mebik)2(NCX)2] Complexes: Variable-Temperature Structural, Magnetic, and Optical Studies (X = S, Se; Mebik = bis(1-methylimidazol-2-yl)ketone)

Author

Siddhartha De, Lise-Marie Chamoreau, Hasnaa El Said, Yanling Li, Alexandrine Flambard, Marie-Laure Boillot, Subrata Tewary, Gopalan Rajaraman, and Rodrigue Lescouëzec

Subjects
spin crossover, iron(II) complexes, photomagnetism, DFT, B3LYP/B3LYP*, Chemistry, QD1-999
Abstract

Two new iron(II) neutral complexes of bis(1-methylimidazol-2-yl)ketone (Mebik) with molecular formula [FeII(Mebik)2(NCS)2] (1) and [FeII(Mebik)2(NCSe)2] (2) have been synthesized and characterized by magnetic measurements, single-crystal X-ray diffraction, and solid state UV-vis spectroscopy. The temperature dependent magnetic susceptibility measurements of crystalline samples of both compound show the occurrence of a gradual spin transition centered at T1/2 = 260 K and 326 K, respectively. The crystal structures of both compounds were determined at different temperatures, below and above the transition, in order to detect the structural changes associated with the spin transition. The main structural modifications, when passing from the low-spin to the high-spin form, consist of an important lengthening of the Fe-N(Mebik) and Fe-N (C-S/Se) distances (by ca. 0.20 and 0.18 Å, respectively) and a noticeable variation of the N-Fe-N angles, leading to a more distorted [Fe-N6] octahedron. The spin-transition phenomenon also affects the optical properties, with significant decrease of the intensity of the Metal-to-Ligand charge transfer band upon increasing the temperature. Finally, both complexes exhibit a light-induced excited spin-state trapping under laser light irradiation at low temperature. DFT calculations were also carried out on these complexes in order to rationalize the theoretically predicted magnetic and optical behavior with those of the experimental one. The results clearly highlights the dramatic alteration of the magneto-structural behavior of the tris-chelate [FeII(Mebik)3]2+ spin-crossover complex upon substituting one Mebik with NCS and NCSe ligands.

Published
2018
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11. Field-induced single ion magnet behaviour of discrete and one-dimensional complexes containing [bis(1-methylimidazol-2-yl)ketone]-cobalt(II) building units

Author

Yanling Li, Rodrigue Lescouëzec, Joan Cano, Maria-Gabriela Alexandru, Miguel Julve, Hasnaa El Said, Diana Visinescu, Lise-Marie Chamoreau, Sergiu Shova, Juan-Ramón Jiménez, Jurgen von Bardeleben, Buqing Xu, 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 des Nanosciences de Paris (INSP), Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), 'Petru Poni' Institute of Macromolecular Chemistry, Institute of Physical Chemistry 'Ilie Murgulescu' Romanian Academy (ICF), Universitatea Politehnica din Bucuresti [Bucarest, Roumanie] (UPB), Instituto de Ciencia Molecular (ICMol), and Universitat de València (UV)

Subjects
Denticity, Materials science, Pyrazine, 010405 organic chemistry, chemistry.chemical_element, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, law.invention, Inorganic Chemistry, Magnetization, Crystallography, Paramagnetism, Magnetic anisotropy, chemistry.chemical_compound, chemistry, law, [CHIM]Chemical Sciences, Molecule, Electron paramagnetic resonance, Cobalt
Abstract

International audience; We describe herein the first examples of six-coordinate CoII single-ion magnets (SIMs) based on the β-diimine Mebik ligand [Mebik = bis(1-methylimidazol-2-yl)ketone]: two mononuclear [CoII(Rbik)2L2] complexes and one mixed-valence {CoIII2CoII}n chain of formulas [CoII(Mebik)(H2O)(dmso)(μ-NC)2CoIII2(μ-2,5-dpp)(CN)6]n·1.4nH2O (3) [L = NCS (1), NCSe (2) and 2,5-dpp = 2,5-bis(2-pyridyl)pyrazine (3)]. Two bidentate Mebik molecules plus two monodentate N-coordinated pseudohalide groups in cis positions build somewhat distorted octahedral surroundings around the high-spin cobalt(II) ions in 1 and 2. The diamagnetic [CoIII2(μ-2,5-dpp)(CN)8]2− metalloligand coordinates the paramagnetic [CoII(Mebik)(H2O)(dmso)]2+ complex cations in a bis-monodentate fashion to afford neutral zigzag heterobimetallic chains in 3. Ab initio calculations, and cryomagnetic dc (2.0–300 K) and ac (2.0–12 K) measurements as well as EPR spectroscopy for 1–3 show the existence of magnetically isolated high-spin cobalt(II) ions with D values of 59.84–89.90 (1), 66.32–93.90 (2) and 70.40–127.20 cm−1 (3) and field-induced slow relaxation of the magnetization, being thus new examples of SIMs with transversal magnetic anisotropy. The analysis of their relaxation dynamics reveals that the relaxation of the magnetization occurs by the Raman (with values of the n parameter covering the range 6.0–6.8) and direct spin-phonon processes.

Published
2021

13. Appealing Copper(I) and Silver(I) Coordination Polymers with an Unprecedented Betainoid Assembling Ligand

Author

Lise-Marie Chamoreau, Dylan Amelot, Jamal Moussa, Hani Amouri, and Ammar Hassoun

Subjects
chemistry.chemical_classification, Materials science, chemistry, 010405 organic chemistry, Ligand, chemistry.chemical_element, Polymer, 010402 general chemistry, 01 natural sciences, Combinatorial chemistry, Copper, 0104 chemical sciences
Abstract

Two coordination polymers of coinage metals with a rare pyridinium-betainoid L assembling ligand are reported. These polymers are obtained by self-assembly of the linker L and copper(I) or silver(I) ions in acetonitrile. The compounds were characterized by spectroscopic methods and by elemental analysis. The solid-state structures were unambiguously confirmed by single crystal diffraction studies. These assemblies exhibit original helicoidal arrangements. The UV-Vis. absorption and photoluminescence properties are reported as well.

Published
2019

14. Mapping C−H×××M Interactions in Confined Spaces: (a-ICyD Me )Au, Ag, Cu Complexes Reveal 'Contra-electrostatic H-bonds' Masquerading as Anagostic Interactions

Author

Guangcan Xu, Igor V. Alabugin, Sylvain Roland, Xiaolei Zhu, Olivia Bistri-Aslanoff, Matthieu Sollogoub, Gabriel dos Passos Gomes, Lise-Marie Chamoreau, Yongmin Zhang, University of Toronto, Sorbonne Université (SU), Florida State University [Panama City], 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
C-H metal interactions, NHC, Coinage metals, Electron, 010402 general chemistry, 01 natural sciences, Catalysis, Metal, H-bonds, [CHIM]Chemical Sciences, Confined space, cyclodextrins, 010405 organic chemistry, Hydrogen bond, Chemistry, anagostic interactions, Organic Chemistry, General Chemistry, Electrostatics, 0104 chemical sciences, coinage metals, Crystallography, Main group element, Covalent bond, visual_art, visual_art.visual_art_medium, Confinement
Abstract

International audience; What happens when a C-H bond is forced to interact with unpaired pairs of electrons at a positively charged metal? Such interactions can be considered as "contra-electrostatic" H-bonds, which combine the familiar orbital interaction pattern characteristic for the covalent contribution to the conventional H-bonding with an unusual contra-electrostatic component. While electrostatics is strongly stabilizing component in the conventional C-H … X bonds where X is an electronegative main group element, it is destabilizing in the C-H … M contacts when M is Au(I), Ag(I), or Cu(I) of NHC-M-Cl systems. Such remarkable C-H … M interaction became experimentally accessible within (α-ICyD Me )MCl, NHC-Metal complexes embedded into cyclodextrins. Computational analysis of the model systems suggests that the overall interaction energies are relatively insensitive to moderate variations in the directionality of interaction between a C-H bond and the metal center, indicating stereoelectronic promiscuity of fully filled set of d -orbitals. A combination of experimental and computational data demonstrates that metal encapsulation inside the cyclodextrin cavity forces the C-H bond to point toward the metal, and reveals a still attractive "contra-electrostatic" H-bonding interaction.

Published
2021

15. Towards redox-switchable organocatalysts based on bidentate halogen bond donors

Author

Claire Fave, Stefan M. Huber, Lise-Marie Chamoreau, M. Gartmann, Elric Engelage, Bernd Schöllhorn, H. Hijazi, Laboratoire d'Electrochimie Moléculaire (LEM (UMR_7591)), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Paris (UP), Institut 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'Ecologie Microbienne - UMR 5557 (LEM), Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-Ecole Nationale Vétérinaire de Lyon (ENVL)-VetAgro Sup - Institut national d'enseignement supérieur et de recherche en alimentation, santé animale, sciences agronomiques et de l'environnement (VAS)-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)

Subjects
inorganic chemicals, Denticity, Halogen bond, 010405 organic chemistry, Chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, General Physics and Astronomy, Halide, [CHIM.CATA]Chemical Sciences/Catalysis, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, Electrochemistry, 01 natural sciences, Redox, Medicinal chemistry, 0104 chemical sciences, Catalysis, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, [CHIM]Chemical Sciences, Titration, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Lewis acids and bases, Physical and Theoretical Chemistry
Abstract

International audience; Redox-active bidentate halogen bond donors based on halopyridinium groups as halogen-bond donating units were synthesized and their structures were elucidated by X-ray diffraction analyses and DFT calculations. Via reversible twofold reduction, these dicationic species can be transformed to neutral compounds which should be much weaker Lewis acids. The corresponding electrochemical data were obtained, and CV as well as UV-vis and NMR techniques were also used to determine binding constants of these halogen bond donors to halides. While all titrations agree on the relative order of binding strengths (with chloride being bound strongest), there are marked deviations in the overall affinity constants which are discussed. In contrast to earlier azo-bridge analogues, the ethylene-linked variants presented herein do not oxidize halides, and thus the novel halogen bond donors could also be used as Lewis acidic organocatalysts in a halide abstraction benchmark reaction, yielding a performance similar to bis(haloimidazolium)-derived catalysts.

Published
2021

16. The atypical hysteresis of [Fe(C6F5Tp)2]: Overlay of spincrossovers and symmetry-breaking phase transition

Author

Lise-Marie Chamoreau, David Kreher, Amina Benchohra, Rodrigue Lescouëzec, Nathalie Guillou, Benoit Baptiste, Yanling Li, Erik Elkaim, 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 minéralogie, de physique des matériaux et de cosmochimie (IMPMC), Muséum national d'Histoire naturelle (MNHN)-Institut de recherche pour le développement [IRD] : UR206-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Synchrotron SOLEIL (SSOLEIL), Centre National de la Recherche Scientifique (CNRS), Institut Lavoisier de Versailles (ILV), Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), and Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Phase transition, Materials science, Spin transition, molecular magnetism, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Catalysis, Annealing (glass), Crystal, Spin crossover, [CHIM]Chemical Sciences, Symmetry breaking, Molecular switch, Condensed matter physics, 010405 organic chemistry, General Medicine, General Chemistry, 021001 nanoscience & nanotechnology, 0104 chemical sciences, molecular switch, Hysteresis, spin-crossover, coordination chemistry, 0210 nano-technology
Abstract

International audience; The [Fe II (C6F5Tp)2] spin-crossover complex is an atypical molecular switch, which can be converted upon annealing between two archetypal spin-crossover behaviours: from an extremely gradual spin-crossover to a broad hysteretic spin-transition (of ca. 65 K). The hysteresis shows an uncommon "rounded shape" that is reproducible upon cycling temperature. In depth structural studies reveal a first crystal phase transition, which occurs upon melting and recrystallizing at high temperature. This first irreversible transition is associated with a radical change in the crystal packing. More importantly, the "rounded and broad" hysteretic transition is shown to occurs in a noncooperative SCO system and is associated with the occurrence of a symmetry-breaking phase transition that appears when roughly ca. 50% of the SCO complexes are switched.

Published
2021

17. Mapping C-H⋅⋅⋅M Interactions in Confined Spaces: (α-ICyD

Author

Gabriel, Dos Passos Gomes, Guangcan, Xu, Xiaolei, Zhu, Lise-Marie, Chamoreau, Yongmin, Zhang, Olivia, Bistri-Aslanoff, Sylvain, Roland, Igor V, Alabugin, and Matthieu, Sollogoub

Abstract

What happens when a C-H bond is forced to interact with unpaired pairs of electrons at a positively charged metal? Such interactions can be considered as "contra-electrostatic" H-bonds, which combine the familiar orbital interaction pattern characteristic for the covalent contribution to the conventional H-bonding with an unusual contra-electrostatic component. While electrostatics is strongly stabilizing component in the conventional C-H⋅⋅⋅X bonds where X is an electronegative main group element, it is destabilizing in the C-H⋅⋅⋅M contacts when M is Au(I), Ag(I), or Cu(I) of NHC-M-Cl systems. Such remarkable C-H⋅⋅⋅M interaction became experimentally accessible within (α-ICyD

Published
2021

18. The Atypical Hysteresis of [Fe(C

Author

Amina, Benchohra, Yanling, Li, Lise-Marie, Chamoreau, Benoit, Baptiste, Erik, Elkaïm, Nathalie, Guillou, David, Kreher, and Rodrigue, Lescouëzec

Abstract

The [Fe

Published
2021

19. Building responsive materials by assembling {Fe4Co4} switchable molecular cubes

Author

Rodrigue Lescouëzec, Damien Dambournet, Olaf J. Borkiewicz, Yanling Li, Juan-Ramón Jiménez, Alexandrine Flambard, Laurent Lisnard, Laure Catala, Jana Glatz, Antoine Tissot, Rémi Plamont, Lise-Marie Chamoreau, Amina Benchohra, Marie-Laure Boillot, Qui Pham Xuan, Institut Parisien de Chimie Moléculaire (IPCM), Chimie Moléculaire de Paris Centre (FR 2769), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), PHysicochimie des Electrolytes et Nanosystèmes InterfaciauX (PHENIX), Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Réseau sur le stockage électrochimique de l'énergie (RS2E), Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA), Argonne National Laboratory [Lemont] (ANL), 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 des Matériaux Poreux de Paris (IMAP ), Département de Chimie - ENS Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), 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), École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), and Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Materials science, Molecular model, 010405 organic chemistry, Ligand, Precipitation (chemistry), General Chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, Scorpionate ligand, 01 natural sciences, 0104 chemical sciences, Electron transfer, Paramagnetism, Chemical engineering, Materials Chemistry, Cube
Abstract

International audience; Responsive materials that can answer to chemical or physical external stimuli offer numerous prospects in material science. Here, we have elaborated a two-step synthetic approach that allows incorporating molecular cubic switches into a polymeric material. Firstly, a preformed half-capped, Cs+-templated {Fe4Co4} cyanido-polymetallic cubic unit (“pro-cube”) is obtained and proven to be stable in solution, as demonstrated by paramagnetic NMR. Secondly, the reaction of the pro-cube with a ditopic scorpionate ligand enables the precipitation of a polymeric network containing the cubic unit. Furthermore, the adequately chosen ditopic ligand that coordinates the Co ions of the pro-cube allows us to preserve the switchable properties of the cubic unit. Indeed, the magnetic properties of the polymeric material compare well with those of the molecular cubic model that is obtained by reacting a non-bridging scorpionate ligand, and that was prepared as a reference. Both the polymeric material and the molecular model cube show a thermally-induced metal–metal electron transfer near room temperature. Interestingly, the magnetic state of the polymeric material is shown to depend on its hydration state, indicating its capability to act as a chemo-sensor.

Published
2021

20. Solvothermal synthesis, structure and magnetic properties of heterometallic coordination polymers based on a phenolato-oxamato co-bidentate-tridentate ligand

Author

Ang Li, Yanling Li, Laurent Lisnard, Lise-Marie Chamoreau, Yves Journaux, Benoit Baptiste, Institut Parisien de Chimie Moléculaire (IPCM), Chimie Moléculaire de Paris Centre (FR 2769), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Equipe de Recherche en Matériaux Moléculaires et Spectroscopies (ERMMES), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Chimie Moléculaire de Paris Centre (FR 2769), Institut de minéralogie, de physique des matériaux et de cosmochimie (IMPMC), Muséum national d'Histoire naturelle (MNHN)-Institut de recherche pour le développement [IRD] : UR206-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), and Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Chimie Moléculaire de Paris Centre (FR 2769)

Subjects
chemistry.chemical_classification, Denticity, Tridentate ligand, 010405 organic chemistry, Ligand, Chemistry, Solvothermal synthesis, Polymer, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Inorganic Chemistry, Crystallography, Antiferromagnetism, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Isostructural, Powder diffraction
Abstract

International audience; The use of solvothermal conditions has succesfully led to the preparation of heterometallic 1D coordination polymers from a co-bidentate-tridentate phenolato-oxamato ligand. The reaction of the N-(2-hydoxyphenyl)oxamic acid (ohpma) with acetate salts of transition metal ions at 80°C has yielded the heterobimetallic [Cu(ohpma)M(OAc)(DMF)2] (M = Co (1); Mn (2)) and the heterotrimetallic [Cu(ohpma)Co0.57Mn0.43(OAc)(DMF)2] (3) chain compounds. Single-crystal and powder diffraction studies show that the polymers are isostructural. Magnetic studies suggest the existence of an inter-chain two-dimensional antiferromagnetic interaction taking place in compounds 1-3.

Published
2020

21. Insights into the antiproliferative mechanism of (C^N)-chelated half-sandwich iridium complexes

Author

Annie Munier, Serge Thorimbert, Michèle Salmain, Lise-Marie Chamoreau, Joëlle Sobczak-Thépot, Jeremy M. Zimbron, Anthi Karaiskou, Candice Botuha, Robin Ramos, CHU Saint-Antoine [AP-HP], Assistance publique - Hôpitaux de Paris (AP-HP) (AP-HP)-Sorbonne Université (SU), Chemical Biology (CHEMBIO), 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)-Chimie Moléculaire de Paris Centre (FR 2769), 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
Models, Molecular, Stereochemistry, Cell Survival, Antineoplastic Agents, Apoptosis, [CHIM.THER]Chemical Sciences/Medicinal Chemistry, Oxidative phosphorylation, Oxazoline, 010402 general chemistry, Iridium, 01 natural sciences, Inorganic Chemistry, HeLa, 03 medical and health sciences, chemistry.chemical_compound, Structure-Activity Relationship, Coordination Complexes, medicine, Humans, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Chelation, Cytotoxicity, 030304 developmental biology, Cell Proliferation, 0303 health sciences, biology, Dose-Response Relationship, Drug, Molecular Structure, Chemistry, Ligand, Metallacycle, biology.organism_classification, 0104 chemical sciences, Mechanism of action, medicine.symptom, Drug Screening Assays, Antitumor, HeLa Cells
Abstract

International audience; Transition metal-based anticancer compounds, as an alternative to platinum derivatives, are raising scientific interest as they may present distinct although poorly understood mechanisms of action. We used a structure–activity relationship-based methodology to investigate the chemical and biological features of a series of ten (C^N)-chelated half-sandwich iridiumIII complexes of the general formula [IrCp*(phox)Cl], where (phox) is a 2-phenyloxazoline ligand forming a 5-membered metallacycle. This series of compounds undergoes a fast exchange of their chlorido ligand once solubilised in DMSO. They were cytotoxic to HeLa cells with IC50 values in the micromolar range and induced a rapid activation of caspase-3, an apoptosis marker. In vitro, the oxidative power of all the complexes towards NADH was highlighted but only the complexes bearing substituents on the oxazoline ring were able to produce H2O2 at the micromolar range. However, we demonstrated using a powerful HyPer protein redox sensor-based flow cytometry assay that most complexes rapidly raised intracellular levels of H2O2. Hence, this study shows that oxidative stress can partly explain the cytotoxicity of these complexes on the HeLa cell line and gives a first entry to their mechanism of action.

Published
2020

22. Permethylated NHC-capped aand b-cyclodextrins (ICyD Me ) Regioselective and enantioselective gold-catalysis in pure water

Author

Louis Fensterbank, Lise-Marie Chamoreau, Guangcan Xu, Yongmin Zhang, Xiaolei Zhu, Virginie Mouriès-Mansuy, Matthieu Sollogoub, Sylvain Roland, Olivia Bistri-Aslanoff, 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
chemistry.chemical_classification, Cyclodextrin, catalysis, 010405 organic chemistry, Organic Chemistry, water, Enantioselective synthesis, chemistry.chemical_element, Regioselectivity, General Chemistry, β cyclodextrins, cavity, 010402 general chemistry, 01 natural sciences, Copper, Combinatorial chemistry, 0104 chemical sciences, Catalysis, Cycloisomerization, chemistry, [CHIM]Chemical Sciences, N-heterocyclic carbene
Abstract

A series of water-soluble encapsulated copper(I), silver(I) or gold(I) complexes based on NHC-capped permethylated cyclodextrins (ICyDMe ) were developed and used as catalysts in pure water for hydration, lactonization, hydroarylation and cycloisomerization reactions. ICyDMe ligands gave cavity-based high regioselectivity in hydroarylations, and high enantioselectivities in gold-catalyzed cycloisomerizations reactions giving up to 98 % ee in water. These ICyDMe are therefore useful ligands for selective catalysis in pure water.

Published
2020

23. Thermo and Electro-Switchable Cs⊂{Fe 4 -Fe 4 } Cubic Cage: Spin-Transition and Electrochromism

Author

Lise-Marie Chamoreau, Azzedine Bousseksou, Jana Glatz, Jean-Francois Meunier, Alexandrine Flambard, Rodrigue Lescouëzec, Institut Parisien de Chimie Moléculaire (IPCM), Chimie Moléculaire de Paris Centre (FR 2769), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de chimie de coordination (LCC), Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), and Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Valence (chemistry), Materials science, 010405 organic chemistry, Metals and Alloys, Solid-state, Spin transition, General Chemistry, 010402 general chemistry, 01 natural sciences, Catalysis, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Electronic states, Chemical physics, Electrochromism, Materials Chemistry, Ceramics and Composites, Molecule, [CHIM]Chemical Sciences, Cage
Abstract

International audience; A mixed valence Cs⊂{Fe 4-Fe 4 } cyanido-cube was synthesized and structurally characterized. The molecule, which is robust in solution, shows a remarkable electronic versatility. Electrochromic properties associated with nine different electronic states are observed in solution together with a thermo-induced spin-transition in the solid state. Molecular switches, i.e. molecules able to change their physical (optical, magnetic, etc.) properties under external stimuli are receiving intense research efforts because of their potential application in the fabrication of functional materials or nano-devices.

Published
2020

24. A bis-polydentate oxamate-based achiral ligand able to stabilize a macrocyclic mixed valence compound or induce a 1D helical chain

Author

Christophe Desmarets, Yves Journaux, Lise-Marie Chamoreau, Laurent Lisnard, Ang Li, Yanling Li, Equipe de Recherche en Matériaux Moléculaires et Spectroscopies (ERMMES), 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)-Chimie Moléculaire de Paris Centre (FR 2769), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Chimie Moléculaire de Paris Centre (FR 2769), École normale supérieure - Paris (ENS Paris)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Ecole Nationale Supérieure de Chimie de Paris- Chimie ParisTech-PSL (ENSCP)-ESPCI ParisTech-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS Paris)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Ecole Nationale Supérieure de Chimie de Paris- Chimie ParisTech-PSL (ENSCP)-ESPCI ParisTech-Centre National de la Recherche Scientifique (CNRS), École normale supérieure - Paris (ENS Paris)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Ecole Nationale Supérieure de Chimie de Paris- Chimie ParisTech-PSL (ENSCP)-ESPCI ParisTech-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS Paris)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Ecole Nationale Supérieure de Chimie de Paris- Chimie ParisTech-PSL (ENSCP)-ESPCI ParisTech-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Chimie Moléculaire de Paris Centre (FR 2769), and Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
chemistry.chemical_classification, Valence (chemistry), Denticity, 010405 organic chemistry, Chemistry, chemistry.chemical_element, 010402 general chemistry, 01 natural sciences, Copper, Helical chain, 0104 chemical sciences, Coordination complex, Ion, Inorganic Chemistry, Crystallography, Antiferromagnetism, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Cobalt
Abstract

International audience; The reaction of the N-(2-hydroxyphenyl)oxamate ligand (ohpma) has been investigated with cobalt(II) and copper(II) ions. It has led to two coordination compounds, (TMA) 3 [{Co III (ohpma) 2 Co II (MeOH) 2 } 3 ]·10H 2 O·5MeOH (1) and (HNEt 3)[Cu(ohpma)] (2). Both compounds have been characterized by single-crystal X-ray diffraction and magnetometry. The X-ray diffraction studies have revealed atypical structures that are not commonly observed in oxamate coordination chemistry with a macrocyclic arrangement for the mixed-valence cobalt-based complex 1, and a helical chiral chain for compound 2. In the latter, the bis-polydentate nature of the (ohpma) 3-ligand with distinct tridentate and bidentate coordination sites creates a chirogenic center on the copper ion. The investigation of the magnetic properties shows a field-induced single-molecule magnet behavior for complex 1, while antiferromagnetic interactions dominate the behavior of 2.

Published
2020

25. Thermo- and electro-switchable Cs⊂{Fe

Author

Jana, Glatz, Lise-Marie, Chamoreau, Alexandrine, Flambard, Jean-Francois, Meunier, Azzedine, Bousseksou, and Rodrigue, Lescouëzec

Abstract

A mixed valence Cs⊂{Fe4-Fe4} cyanido-cube was synthesized and structurally characterized. The molecule, which is robust in solution, shows remarkable electronic versatility. Electrochromic properties associated with nine different electronic states are observed in solution together with a thermo-induced spin-transition in the solid state.

Published
2020

26. Dual switchable molecular tweezers incorporating anisotropic Mn

Author

Benjamin, Doistau, Lorien, Benda, Jean-Louis, Cantin, Olivier, Cador, Fabrice, Pointillart, Wolfgang, Wernsdorfer, Lise-Marie, Chamoreau, Valérie, Marvaud, Bernold, Hasenknopf, and Guillaume, Vives

Abstract

An alternative strategy for the synthesis of terpyridine based switchable molecular tweezers has been developed to incorporate anisotropic Mn(iii)-salphen complexes. The free ligand was synthesized using a building block strategy based on Sonogashira coupling reactions and was then selectively metalated with manganese in a last step. The conformation of the tweezers was switched from an open 'W' shaped form to a closed 'U' form by Zn(ii) coordination to the terpyridine unit bringing the two Mn-salphen moieties in close spatial proximity as confirmed by X-ray crystallography. An alternate switching mechanism was observed by the intercalation of a bridging cyanide ligand between the two Mn-salphen moieties that resulted in the closing of the tweezers. These dual stimuli are attractive for achieving multiple controls of the mechanical motion of the tweezers. A crystallographic structure of unexpected partially oxidized closed tweezers was also obtained. One of the two Mn-salphen moieties underwent a ligand-centered oxidation of an imino to an amido group allowing an intramolecular Mn-Oamide-Mn linkage. The magnetic properties of the manganese(iii) dimers were investigated to evaluate the magnetic exchange interaction and analyze the single molecule magnet behavior.

Published
2020

27. Mapping C−H•••M interactions in confined spaces: (α-ICyDᴹᵉ)Au, Ag, Cu complexes reveal 'contra-electrostatic H-bonds' masquerading as anagostic interactions

Author

Igor V. Alabugin, Sylvain Roland, Xiaolei Zhu, Lise-Marie Chamoreau, Olivia Bistri Aslanoff, Matthieu Sollogoub, Yongmin Zhang, Guangcan Xu, and Gabriel dos Passos Gomes

Subjects
Metal, chemistry.chemical_classification, Crystallography, Main group element, Cyclodextrin, Covalent bond, Chemistry, visual_art, visual_art.visual_art_medium, Directionality, Electron, Electrostatics, Confined space
Abstract

What happens when a C−H bond is forced to interact with unpaired pairs of electrons at a positively charged metal? Such interactions can be considered as “contra-electrostatic” H-bonds, which combine the familiar orbital interaction pattern characteristic for the covalent contribution to the conventional H-bonding with an unusual contra-electrostatic component. While electrostatics is strongly stabilizing component in the conventional C−H•••X bonds where X is an electronegative main group element, it is destabilizing in the C−H•••M contacts when M is Au(I), Ag(I), or Cu(I) of NHC−M−Cl systems. Such remarkable C−H•••M interaction became experimentally accessible within (α-ICyDMe)MCl, NHC−Metal complexes embedded into cyclodextrins. Computational analysis of the model systems suggests that the overall interaction energies are relatively insensitive to moderate variations in the directionality of interaction between a C−H bond and the metal center, indicating stereoelectronic promiscuity of fully filled set of d-orbitals. A combination of experimental and computational data demonstrates that metal encapsulation inside the cyclodextrin cavity forces the C−H bond to point toward the metal, and reveals a still attractive “contra-electrostatic” H-bonding interaction.

Published
2020

28. Permethylated NHC-Capped α- and β-Cyclodextrins (ICyD

Author

Xiaolei, Zhu, Guangcan, Xu, Lise-Marie, Chamoreau, Yongmin, Zhang, Virginie, Mouriès-Mansuy, Louis, Fensterbank, Olivia, Bistri-Aslanoff, Sylvain, Roland, and Matthieu, Sollogoub

Abstract

A series of water-soluble encapsulated copper(I), silver(I) or gold(I) complexes based on NHC-capped permethylated cyclodextrins (ICyD

Published
2020

29. Mapping the coordination space for C−H•••M interactions in confined spaces: (α-ICyDᴹᵉ)Au, Ag, Cu complexes reveal 'contra-electrostatic H-bonds' masquerading as anagostic interactions

Author

Yongmin Zhang, Guangcan Xu, Olivia Bistri Aslanoff, Lise-Marie Chamoreau, Matthieu Sollogoub, Igor V. Alabugin, Sylvain Roland, Gabriel dos Passos Gomes, and Xiaolei Zhu

Subjects
chemistry.chemical_classification, Metal, Crystallography, Cyclodextrin, chemistry, Main group element, Covalent bond, visual_art, visual_art.visual_art_medium, Directionality, Electron, Electrostatics, Confined space
Abstract

What happens when a C−H bond is forced to interact with unpaired pairs of electrons at a positively charged metal? Such interactions can be considered as “contra-electrostatic” H-bonds, which combine the familiar orbital interaction pattern characteristic for the covalent contribution to the conventional H-bonding with an unusual contra-electrostatic component. Whereas electrostatics is strongly stabilizing in the conventional C−H•••X bonds where X is an electronegative main group element, it is destabilizing in the C−H•••M contacts when M is Au(I), Ag(I), or Cu(I) of NHC−M−Cl systems. Such remarkable C−H•••M interaction became experimentally accessible within (a-ICyDMe)MCl, NHC−Metal complexes embedded into cyclodextrins. Computational analysis of the model systems suggests that the overall interaction energies are relatively insensitive to moderate variations in the directionality of interaction between a C−H bond and the metal center, indicating stereoelectronic promiscuity of fully filled set of d-orbitals. A combination of experimental and computational data demonstrates that metal encapsulation inside the cyclodextrin cavity forces the C−H bond to point toward the metal, and reveals a still attractive “contra-electrostatic” H-bonding interaction.

Published
2020

30. Electron Transfer in the Cs⊂{Mn 4 Fe 4 } Cubic Switch: a Soluble Molecular Model of the MnFe Prussian-Blue Analogues

Author

Azzedine Bousseksou, Lise-Marie Chamoreau, Jean-François Meunier, Geoffrey Gontard, Jana Glatz, Rodrigue Lescouëzec, Juan-Ramón Jiménez, Amina Benchohra, Institut Parisien de Chimie Moléculaire (IPCM), Chimie Moléculaire de Paris Centre (FR 2769), Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), and Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Molecular switch, Prussian blue, Materials science, 010405 organic chemistry, Magnetism, chemistry.chemical_element, General Medicine, General Chemistry, 010402 general chemistry, 01 natural sciences, Redox, Catalysis, 0104 chemical sciences, Electron transfer, Crystallography, chemistry.chemical_compound, chemistry, Electrochromism, Caesium, Molecule, [CHIM.COOR]Chemical Sciences/Coordination chemistry
Abstract

International audience; A mixed-valence {MnII3 MnIII FeII2 FeIII2} cyanidebridged molecular cube hosting a caesium cation, Cs⊂ - {Mn4Fe4}, was synthesized and structurally characterized by X-ray diffraction. Cyclic-voltammetry measurements show that its electronic state can be switched between five different redox states, which results in a remarkable lectrochromic effect. Magnetic measurements on fresh samples point to the occurrence of a spin-state change near room temperature, which could be ascribed to a metal-to-metal electron transfer converting the {FeII-CN-MnIII} pair into a {FeIII-CN-MnII} pair. This feature was only previously observed in the polymeric MnFe Prussian-blue analogues (PBAs). Moreover, this novel switchable molecule proved to be soluble and stable in organic solvents, paving the way for its integration into advanced materials.

Published
2020

31. Investigation of charge transport properties of [1]Benzothieno[3,2-b][1]-benzothiophene single-crystals in field-effect transistor configuration

Author

David Kreher, Fabrice Mathevet, Emmanuelle Lacaze, Clément Livache, Jean Charles Ribierre, Sébastien Sanaur, Lise-Marie Chamoreau, Xiao Liu, Lydia Sosa-Vargas, Xiaolu Su, Emmanuel Lhuillier, 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), Physico-chimie et dynamique des surfaces (INSP-E6), Institut des Nanosciences de Paris (INSP), Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Ecole des Mines de Saint-Etienne (Institut Mines-Télécom (IMT)) (Mines Saint-Etienne ), Zhejiang University of Technology, China Scholarship Council, China, and the CNRS (PICS N°88085), European Project: 756225,blackQD, École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), École des Mines de Saint-Étienne (Mines Saint-Étienne MSE), and Institut Mines-Télécom [Paris] (IMT)

Subjects
Diffraction, Electron mobility, Materials science, Scanning electron microscope, Analytical chemistry, 02 engineering and technology, Substrate (electronics), 010402 general chemistry, 01 natural sciences, law.invention, Biomaterials, chemistry.chemical_compound, Optical microscope, law, Materials Chemistry, Electrical and Electronic Engineering, Transistor, Benzothiophene, [CHIM.MATE]Chemical Sciences/Material chemistry, General Chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, 0104 chemical sciences, Electronic, Optical and Magnetic Materials, chemistry, Field-effect transistor, 0210 nano-technology
Abstract

International audience; Single-crystals of unsubstituted [1]Benzothieno[3,2-b][1]-benzothiophene (BTBT) were prepared by physical vapor transport deposition (VTP). The packing structure and morphology of the crystals were studied by X-ray diffraction (XRD), polarized optical microscopy (POM), scanning electron microscopy (SEM) and atomic force microscopy (AFM). The charge transport properties of BTBT single-crystals were also investigated via bottom contact/bottom gate (BC/BG) organic field-effect transistors (OFETs) on both SiO2 and n-octadecyltrichlorosilane (OTS) treated surfaces. A maximum hole mobility value of 0.032 cm2V−1s−1 was measured on the OTS substrate. In addition, single-crystal OFETs with ion gel top gate (TG) configuration were also investigated for low voltage operation. This work represents the first investigation of charge carrier mobility of a simple BTBT in transistor configuration and highlights the essential role of the BTBT substitution in charge transport properties.

Published
2020
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32. Dual switchable molecular tweezers incorporating anisotropic Mn-salphen complexes

Author

Lise-Marie Chamoreau, Valérie Marvaud, J. L. Cantin, Bernold Hasenknopf, Olivier Cador, Wolfgang Wernsdorfer, Benjamin Doistau, Guillaume Vives, Fabrice Pointillart, Lorien Benda, Institut Parisien de Chimie Moléculaire (IPCM), Chimie Moléculaire de Paris Centre (FR 2769), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Institut des Nanosciences de Paris (INSP), Sorbonne Université (SU)-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), Circuits électroniques quantiques Alpes (NEEL - QuantECA), Institut Néel (NEEL), 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)-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), Karlsruhe Institute of Technology (KIT), École Normale Supérieure, 15-CE07-0006-01, Agence Nationale de la Recherche, Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), 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), and Circuits électroniques quantiques Alpes (QuantECA)

Subjects
Materials science, 010405 organic chemistry, Intercalation (chemistry), Sonogashira coupling, Crystal structure, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Inorganic Chemistry, chemistry.chemical_compound, Crystallography, chemistry, Intramolecular force, Tweezers, [CHIM]Chemical Sciences, Single-molecule magnet, Terpyridine, Molecular tweezers
Abstract

International audience; An alternative strategy for the synthesis of terpyridine based switchable molecular tweezers has been developed to incorporate anisotropic Mn(iii)-salphen complexes. The free ligand was synthesized using a building block strategy based on Sonogashira coupling reactions and was then selectively metalated with manganese in a last step. The conformation of the tweezers was switched from an open 'W' shaped form to a closed 'U' form by Zn(ii) coordination to the terpyridine unit bringing the two Mn-salphen moieties in close spatial proximity as confirmed by X-ray crystallography. An alternate switching mechanism was observed by the intercalation of a bridging cyanide ligand between the two Mn-salphen moieties that resulted in the closing of the tweezers. These dual stimuli are attractive for achieving multiple controls of the mechanical motion of the tweezers. A crystallographic structure of unexpected partially oxidized closed tweezers was also obtained. One of the two Mn-salphen moieties underwent a ligand-centered oxidation of an imino to an amido group allowing an intramolecular Mn-Oamide-Mn linkage. The magnetic properties of the manganese(iii) dimers were investigated to evaluate the magnetic exchange interaction and analyze the single molecule magnet behavior.

Published
2020

33. Catalyst Design for Alkene Epoxidation by Molecular Analogues of Heterogeneous Titanium-Silicalite Catalysts

Author

Hugo Fouilloux, Albert Solé-Daura, Jorge J. Carbó, Lise-Marie Chamoreau, Anna Proust, Teng Zhang, Christophe M. Thomas, Geoffroy Guillemot, Carine Robert, Josep M. Poblet, Universitat Rovira i Virgili, Institut Parisien de Chimie Moléculaire (IPCM), Chimie Moléculaire de Paris Centre (FR 2769), Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Institut de Recherche de Chimie Paris (IRCP), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ministère de la Culture (MC), Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL), and Departament de Química Física i Inorgànica

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

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

Published
2020

34. Electron Transfer in the Cs⊂{Mn

Author

Juan-Ramón, Jiménez, Jana, Glatz, Amina, Benchohra, Geoffrey, Gontard, Lise-Marie, Chamoreau, Jean-François, Meunier, Azzedine, Bousseksou, and Rodrigue, Lescouëzec

Abstract

A mixed-valence {Mn

Published
2019

35. A chemically-responsive bis-acridinium receptor

Author

Lise-Marie Chamoreau, A. Gosset, Z. Xu, H.-P. Jacquot de Rouville, C. Perruchot, Valérie Heitz, François Maurel, S. Nowak, Guillaume Vives, Interfaces, Traitements, Organisation et Dynamique des Systèmes (ITODYS (UMR_7086)), Université Paris Diderot - Paris 7 (UPD7)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut Parisien de Chimie Moléculaire (IPCM), 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), Glycochimie Organique Biologique et Supramoléculaire (GOBS), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Chimie Moléculaire de Paris Centre (FR 2769), Institut de Chimie de Strasbourg, and Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)

Subjects
POLE 3, 010405 organic chemistry, Chemistry, Solid-state, Triphenylene, macromolecular substances, General Chemistry, Methoxide, 010402 general chemistry, 01 natural sciences, Combinatorial chemistry, Catalysis, 0104 chemical sciences, GOBS, chemistry.chemical_compound, Materials Chemistry, [CHIM]Chemical Sciences, Receptor
Abstract

A dicationic receptor based on two acridinium moieties linked by a triphenylene spacer was studied in solution and in the solid state. Recognition moieties, namely acridiniums, were exploited to evidence a host–guest response of the receptor with electron rich guests. Upon addition of methoxide anions, the formation of the bis-acridane form of the receptor was observed. The chemical responsiveness of the receptor to these anions inhibits its recognition properties towards π-donor guests. In addition, the reversibility of the chemical response was demonstrated under acidic conditions.

Published
2018

36. Successive transitions to modulated states in the {R}Pt2Si2 family

Author

Elen Duverger-Nédellec, Michal Falkowski, Petr Doležal, Volodymyr Buturlim, Alexander Andreev, Jérémy Forté, Lise-Marie Chamoreau, and Ladislav Havela

Subjects
Inorganic Chemistry, Structural Biology, General Materials Science, Physical and Theoretical Chemistry, Condensed Matter Physics, Biochemistry
Published
2021

37. A new {Fe4Co4} soluble switchable nanomagnet encapsulating Cs+: enhancing the stability and redox flexibility and tuning the photomagnetic effect

Author

J. von Bardeleben, Lise-Marie Chamoreau, Yanling Li, M. Tricoire, D. Garnier, Juan-Ramón Jiménez, Yves Journaux, Rodrigue Lescouëzec, Institut Parisien de Chimie Moléculaire (IPCM), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Conception et application de molécules bioactives (CAMB), Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Couches nanométriques : formation, interfaces, défauts (INSP-E5), Institut des Nanosciences de Paris (INSP), Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), and Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Prussian blue, 010405 organic chemistry, Metal ions in aqueous solution, Inorganic chemistry, Photomagnetic effect, Nuclear magnetic resonance spectroscopy, 010402 general chemistry, Photochemistry, 01 natural sciences, Nanomagnet, 0104 chemical sciences, Ion, law.invention, Inorganic Chemistry, chemistry.chemical_compound, chemistry, law, Single-molecule magnet, [CHIM.OTHE]Chemical Sciences/Other, Electron paramagnetic resonance
Abstract

International audience; We report a new cyanide-bridged Cs⊂{Fe4Co4} box, a soluble model of photomagnetic Prussian blue analogues (PBAs). The Cs+ ion has a high affinity for the box and can replace the K+ ion in the preformed K-cube. This exchange is kinetically impeded at room temperature but is accelerated by heating and using the 18-crown-6 ether. The inserted Cs+ ion confers a high robustness to the cube, which withstands boiling, as shown by variable-temperature NMR studies. The stability of this model complex in solution allows the probing of the electronic interaction between the alkali ion and the cyanide cage by using various techniques. These interactions are known to play a role in the photomagnetic behaviour of PBAs. Firstly, the 133Cs NMR spectroscopy proves that there is an electronic communication between the encapsulated alkali ion and the cyanide cage. The measured up-field signal, observed at ca. −200 ppm at 300 K, reveals that a certain amount of spin density is transferred through the bonds from the paramagnetic Co(II) ion to the encapsulated cation. Secondly, cyclovoltammetric studies show that the nature of the inserted ions affects the redox properties of the cage and influences the electronic communication between the metal ions. However, the differences in the electrochemical properties of the K-cube and the Cs-cube remain moderate. As the switching properties are influenced by the redox potential of the Fe and Co centers, similar photomagnetic behaviour is observed, with both of them being highly photomagnetic. This result contrasts strikingly with previous studies on the 3D polymeric PBAs, where the PBAs with a high amount of Cs+ show poor photomagnetic behaviour. In that case, cooperative behaviour likely influences the switching properties. Finally, EPR spectroscopy shows that the K-cube is more anisotropic than the Cs-cube. This difference is reflected in the changes occurring in the slow magnetic relaxation (single molecule magnet behaviour) observed in the two cubes.

Published
2017

38. Photochemical studies on bis-sulfide and -sulfone tethered polyenic derivatives

Author

Sylvie Derenne, Simon Guelen, Louis Fensterbank, Lise-Marie Chamoreau, Virginie Mouriès-Mansuy, Arnaud Huguet, François Volatron, Max Blazejak, Institut Parisien de Chimie Moléculaire (IPCM), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Milieux Environnementaux, Transferts et Interactions dans les hydrosystèmes et les Sols (METIS), Université Pierre et Marie Curie - Paris 6 (UPMC)-École Pratique des Hautes Études (EPHE), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de chimie théorique (LCT), ANR-11-IDEX-0004,SUPER,Sorbonne Universités à Paris pour l'Enseignement et la Recherche(2011), and Université Pierre et Marie Curie - Paris 6 (UPMC)-École pratique des hautes études (EPHE)

Subjects
chemistry.chemical_classification, Cyclodextrin, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Aryl, Organic Chemistry, 010402 general chemistry, Photochemistry, GEOF, 01 natural sciences, Biochemistry, 0104 chemical sciences, Sulfone, Cyclobutane, Adduct, chemistry.chemical_compound, chemistry, Cucurbituril, Moiety, Ladderane, Physical and Theoretical Chemistry
Abstract

International audience; This study focusses on the [2+2]-photocycloaddition of symmetric polyenic system tethered by an aryl bis-sulfide or sulfone platform. Using direct irradiation or photosensibilization, no expected ladderane product was isolated. In most cases, only tricyclic products including a single cyclobutane moeity were formed. Irradiation of bis-acrylic precursors in water with encapsulation by a host (cyclodextrin or cucurbituril) provided a stereoselective access to valuable cyclobutyl adducts.

Published
2017

39. The unusual ring scission of a quinoxaline-pyran-fused dithiolene system related to molybdopterin

Author

Yun Li, Lise-Marie Chamoreau, Thibault Fogeron, Marc Fontecave, Pascal Retailleau, Collège de France - Chaire Chimie des processus biologiques, 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)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie des Substances Naturelles (ICSN), Institut de Chimie du CNRS (INC)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), Institut Parisien de Chimie Moléculaire (IPCM), and Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
010405 organic chemistry, Stereochemistry, Ligand, Molybdopterin, chemistry.chemical_element, 010402 general chemistry, Ring (chemistry), 01 natural sciences, 0104 chemical sciences, Inorganic Chemistry, Molybdopterin cofactor, chemistry.chemical_compound, Quinoxaline, chemistry, Pyran, [CHIM]Chemical Sciences, Cobalt, Bond cleavage
Abstract

The reduction of the dithiolene ligand, qpdt2−, a mimic of the biological molybdopterin cofactor, and the corresponding (η5-cyclopentadienyl)cobalt(III) complex [(qpdt)CoIIICp] was studied. It was found that in both cases an unprecedented ring scission reaction took place in acidic medium. All new reaction products have been spectroscopically and structurally characterized. Plausible mechanisms for the formation of these products were also proposed.

Published
2017

40. Synthesis of Homoditopic Ligands with an Incrementable Rodlike Backbone

Author

Hélène Bertrand, Lise-Marie Chamoreau, Paul Demay-Drouhard, Régis Guillot, and Clotilde Policar

Subjects
010405 organic chemistry, Chemistry, Organic Chemistry, Supramolecular chemistry, Surface modification, Physical and Theoretical Chemistry, 010402 general chemistry, 01 natural sciences, Combinatorial chemistry, 0104 chemical sciences
Abstract

We describe the synthesis of architectures that consist of a symmetrical rodlike oligo(phenylene-ethynylene) (OPE) backbone of incrementable length connected to a pair of classical ligands for metal coordination. OPE spacers decorated with various end groups and incorporating up to seven phenylene-acetylene repeat units were quickly obtained through a bidirectional approach. Efficient further functionalization with useful coordinating groups were achieved. The resulting homoditopic platforms are of interest in numerous fields ranging from supramolecular chemistry to materials science.

Published
2016

41. Tetranuclear [Fe II 2 Fe III 2 ] 2+ molecular switches [Fe II (bik) 2 (N–) 2 ]spin-crossover complexes containing [Fe III (Tp)(CN) 3 ] – metalloligands as N-donor

Author

Lise-Marie Chamoreau, Yanling Li, Abhishake Mondal, Frank Breher, Patrick Herson, Eric Moos, Loïc Toupet, Marylise Buron-Le Cointe, Rodrigue Lescouëzec, Delphine Garnier, 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 Physique de Rennes (IPR), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Centre National de la Recherche Scientifique (CNRS), Institute of Inorganic Chemistry, Karlsruhe Institute of Technology (KIT), 3MET, projectB4Ministère de l'Enseignement supérieur, de la Recherche et de l'InnovationCentre National de la Recherche Scientifique, École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), and Université de Rennes (UR)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Molecular switch, [PHYS]Physics [physics], Valence (chemistry), 010405 organic chemistry, Chemistry, General Chemical Engineering, Cooperativity, Photomagnetic effect, General Chemistry, 010402 general chemistry, 01 natural sciences, Spin-crossover complex, LIESST, 0104 chemical sciences, Fe II, Crystallography, Cyanide ligand, Spin crossover, Excited state, Molecule, Photomagnetism
Abstract

International audience; Three novel mixed valence cyanide-bridged {Fe III 2 Fe II 2 } square complexes were obtained through the self-assembling of [Fe III (Tp)(CN) 3 ] - or [Fe III (Tp*)(CN) 3 ] − cyanido building blocks with the in situ formed [Fe II (bik) 2 (S) 2 ]complex (Tp = hydrotris (pyrazol-1-yl)borate, Tp* = hydrotris (3,5-dimethyl-pyrazol-1-yl)borate, bik = bis(1-methylimidazol-2-yl)ketone, S = solvent). The structures of these three complexes (2, 3 and 4)are reminiscent of that of our previously published square complex {[Fe III (Tp)(CN) 3 ] 2 [Fe II (bik) 2 ] 2 }·[Fe III (Tp)(CN) 3 ] 2 ·18H 2 O·4CH 3 OH (1). They consist of cyanide-bridged square dicationic complexes, ClO 4 − (2 and 3)or BF 4 − (4)counterions and solvate molecules. The FT-IR cyanide stretching vibrations observed at ν CN ≈ 2145–60 cm −1 are typical of {Fe III –CN–Fe II } moieties. The investigation of the magnetic properties of 2 reveals the occurrence of spin-crossover centered at T 1/2 = 227 K. The χ M T variation, ca. 7 cm 3 mol −1 K, reflects the complete spin-state change occurring on both {Fe II (bik)(–NC) 2 } moieties (–NC represents the cyanido building blocks). The Slichter–Drickamer model leads to a weak cooperativity factor, Γ = 1.6 kJ mol −1 (with Γ andlt; 2RT 1/2 ), which reflects the gradual spin-state change. This is in agreement with the molecular structure of 2, which does not present significant intermolecular interactions. The calculated enthalpy and entropy variations associated with the spin-state equilibrium are ΔH = 24 kJ mol −1 and ΔS = 105 J K −1 mol −1 . In contrast, 3 and 4 show only partial spin-crossover in the accessible temperature range (2–400 K)as the T 1/2 are shifted toward higher temperatures (ca. T 1/2 andgt; 400 K). Although no photomagnetic effect is observed for 3, compound 4 shows a moderate increase in the magnetization upon irradiation at low temperature. This phenomenon is ascribed to the light-induced excited spin-state trapping (LIESST)effect. Interestingly, the complex 2 also shows a remarkable LIESST effect, which is observed with different laser lights covering the visible and near-infrared range. The resulting χ M T value obtained in the photoinduced state suggests the occurrence of a ferromagnetic interaction inside the {Fe III –CN–Fe II } units. © 2019 Académie des sciences

Published
2019

42. Polymerization of rac-Lactide Using Achiral Iron Complexes: Access to Thermally Stable Stereocomplexes

Author

Laurent Maron, Xavier Trivelli, Carine Robert, Lise-Marie Chamoreau, Vincent Guérineau, Christophe M. Thomas, Paul Marin, Iker del Rosal, Mathieu J.-L. Tschan, Pierre Haquette, Florence Isnard, Vincenzo Venditto, Institut de Recherche de Chimie Paris (IRCP), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ministère de la Culture (MC), Unité de Glycobiologie Structurale et Fonctionnelle (UGSF), Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), 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 des Substances Naturelles (ICSN), Institut de Chimie du CNRS (INC)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), Laboratoire de physique et chimie des nano-objets (LPCNO), 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 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), INSTM Res Unit, Dept Chem & Biol A Zambelli, Univ Salerno, Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Ministère de la Culture (MC), Unité de Glycobiologie Structurale et Fonctionnelle - UMR 8576 (UGSF), Université de Lille-Centre National de la Recherche Scientifique (CNRS), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Université Toulouse III - Paul Sabatier (UT3), and Université de Toulouse (UT)-Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Homogeneous catalysis, 010402 general chemistry, 01 natural sciences, Catalysis, chemistry.chemical_compound, homogeneous catalysis, iron complexes, lactide, polymers, synthetic methods, [CHIM]Chemical Sciences, ComputingMilieux_MISCELLANEOUS, chemistry.chemical_classification, Lactide, 010405 organic chemistry, General Chemistry, Polymer, Combinatorial chemistry, 0104 chemical sciences, Enantiopure drug, chemistry, Polymerization, Stereoselectivity, Enantiomer
Abstract

Enantiopure poly(lactic acid) (PLA) can form stereocomplexes when enantiomeric PLA chains are mixed in equivalent amounts. Such materials provide interesting features that might be suitable for numerous applications. Despite several advantages, the main drawback of PLA is its narrow window of processing, thus limiting its use for industrial applications. Reported herein are achiral iron complexes, that are highly active, productive, and stereoselective under mild reaction conditions for the ring-opening polymerization of lactide. The corresponding catalytic systems enable the production of stereoblock polymers with high molecular weights, allowing the formation of thermally stable and industrially relevant stereocomplexes.

Published
2019

43. A high-nuclearity metal-cyanide cluster [Mo6Cu14] with photomagnetic properties

Author

Nathalie Bridonneau, Geoffrey Gontard, J. L. Cantin, Valérie Marvaud, Lise-Marie Chamoreau, J. von Bardeleben, Institut Parisien de Chimie Moléculaire (IPCM), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Couches nanométriques : formation, interfaces, défauts (INSP-E5), Institut des Nanosciences de Paris (INSP), Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Edifices PolyMétalliques (E-POM), and Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
[PHYS]Physics [physics], Materials science, 010405 organic chemistry, Cyanide, 010402 general chemistry, Photomagnetism, 01 natural sciences, 7. Clean energy, 0104 chemical sciences, Inorganic Chemistry, Metal, Crystallography, chemistry.chemical_compound, Nanocages, Nuclear magnetic resonance, chemistry, visual_art, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], visual_art.visual_art_medium, Cluster (physics)
Abstract

International audience; A high-nuclearity metal-cyanide cluster [Mo 6 Cu 14 ] has been prepared and its photomagnetic properties investigated. The photoswitchable magnetic phenomenon observed is thermally reversible (T 230 K). In the field of photomagnetism, [Mo 6 Cu 14 ] represents a unique example of nanocage and the highest nuclearity observed so far.

Published
2016

44. A cobalt complex with a bioinspired molybdopterin-like ligand: a catalyst for hydrogen evolution

Author

Lise-Marie Chamoreau, Thibault Fogeron, Tanya K. Todorova, Maria Gómez-Mingot, Yun Li, Jean-Philippe Porcher, Marc Fontecave, and Caroline Mellot-Draznieks

Subjects
010405 organic chemistry, Hydride, Ligand, Molybdopterin, chemistry.chemical_element, Protonation, 010402 general chemistry, Photochemistry, 01 natural sciences, 0104 chemical sciences, Catalysis, Inorganic Chemistry, chemistry.chemical_compound, Crystallography, chemistry, Formate, Cobalt, Derivative (chemistry)
Abstract

Cobalt dithiolene complexes are a new class of H2-evolving catalysts. Here we describe the preparation, the structure and the catalytic activity of an original cobalt complex using a bioinspired ligand, a quinoxaline-pyran-fused dithiolene derivative (qpdt(2-)) that mimics the molybdopterin cofactor present in the active sites of formate dehydrogenases. This complex displays very good activity for electrochemical proton reduction under weak acid conditions in terms of turnover frequency, faradic yields and stability. Density functional theory calculations show that protonation of a nitrogen atom of the ligand decreases overpotentials by 520 mV and H2 formation proceeds via protonation of an intermediate Co-H hydride, with an adjacent S atom of the dithiolene ligand serving as a proton relay.

Published
2016

45. One synthesis: two redox states. Temperature-oriented crystallization of a charge transfer {Fe2Co2} square complex in a {FeIILSCoIIILS}2 diamagnetic or {FeIIILSCoIIHS}2 paramagnetic state

Author

Yanling Li, Siddhartha De, Alexandrine Flambard, Azzedine Bousseksou, Juan-Ramón Jiménez, Lise-Marie Chamoreau, Rodrigue Lescouëzec, and Yves Journaux

Subjects
Condensed matter physics, 010405 organic chemistry, Chemistry, General Chemical Engineering, Charge (physics), General Chemistry, 010402 general chemistry, 01 natural sciences, Redox, Square (algebra), 0104 chemical sciences, law.invention, Crystal, Paramagnetism, Crystallography, law, Phase (matter), Diamagnetism, Crystallization
Abstract

The reaction of [FeIII(Tp)(CN)3]− with [CoII(vbik)2(S)2]2+ leads selectively to the crystallization of cyanide-bridged diamagnetic {FeIILSCoIIILS}2 squares at 5 °C or paramagnetic {FeIIILSCoIIHS}2 ones at 35 °C. The diamagnetic crystal phase can be converted to a paramagnetic one upon heating and it shows photomagnetic effects at low temperature.

Published
2016

46. Cover Feature: Permethylated NHC‐Capped α‐ and β‐Cyclodextrins (ICyD Me ) Regioselective and Enantioselective Gold‐Catalysis in Pure Water (Chem. Eur. J. 68/2020)

Author

Louis Fensterbank, Sylvain Roland, Olivia Bistri-Aslanoff, Lise-Marie Chamoreau, Matthieu Sollogoub, Yongmin Zhang, Xiaolei Zhu, Virginie Mouriès-Mansuy, and Guangcan Xu

Subjects
chemistry.chemical_classification, Cyclodextrin, chemistry, Feature (computer vision), Organic Chemistry, Enantioselective synthesis, Regioselectivity, Cover (algebra), General Chemistry, β cyclodextrins, Combinatorial chemistry, Catalysis
Published
2020

47. Correction: Thermo- and electro-switchable Cs⊂{Fe4–Fe4} cubic cage: spin-transition and electrochromism

Author

Rodrigue Lescouëzec, Jean-Francois Meunier, Azzedine Bousseksou, Alexandrine Flambard, Lise-Marie Chamoreau, and Jana Glatz

Subjects
Materials science, Condensed matter physics, Electrochromism, Materials Chemistry, Metals and Alloys, Ceramics and Composites, Spin transition, General Chemistry, Cage, Catalysis, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials
Abstract

Correction for ‘Thermo- and electro-switchable Cs⊂{Fe4–Fe4} cubic cage: spin-transition and electrochromism’ by Jana Glatz et al., Chem. Commun., 2020, DOI: 10.1039/d0cc04279j.

Published
2020

48. Pyranopterin Related Dithiolene Molybdenum Complexes as Homogeneous Catalysts for CO

Author

Thibault, Fogeron, Pascal, Retailleau, Lise-Marie, Chamoreau, Yun, Li, and Marc, Fontecave

Abstract

Two original dithiolenes, with a pyrazine ring fused with a pyran ring carrying the dithiolene chelate, mimicking molybdopterin (MPT) present in the active site of formate dehydrogenases (FDHs), have been synthesized. The first one mimicks MPT in the dihydropyrazine form while the second mimicks MPT in the more biologically relevant tetrahydropyrazine form. Both have been structurally characterized as a ligand within a cobalt(cyclopentadienyl)(dithiolene) complex. The corresponding MoO(dithiolene)

Published
2018

49. Antiferromagnetic Interactions in Copper(II) µ-Oxalato Dinuclear Complexes: The Role of the Counterion

Author

Michel Verdaguer, Alain Gleizes, Miguel Julve, Lise Marie Chamoreau, Eliseo Ruiz, Centre National de la Recherche Scientifique - CNRS (FRANCE), Institut National Polytechnique de Toulouse - Toulouse INP (FRANCE), Sorbonne Université (FRANCE), Université Toulouse III - Paul Sabatier - UT3 (FRANCE), Universitat de Barcelona - UB (SPAIN), Universitat de Valencia - UV (SPAIN), Centre Interuniversitaire de Recherche et d'Ingénierie des Matériaux - CIRIMAT (Toulouse, France), Institut National Polytechnique de Toulouse - INPT (FRANCE), Instituto de Ciencia Molecular (ICMol), Universitat de València (UV), Centre interuniversitaire de recherche et d'ingenierie des matériaux (CIRIMAT), Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC), Institut Parisien de Chimie Moléculaire (IPCM), Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), and Universitat de Barcelona (UB)

Subjects
Dinuclear complexes, Matériaux, Ferromagnetisme, chemistry.chemical_element, Crystal structure, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, Triclinic crystal system, 010402 general chemistry, 01 natural sciences, Oxalate, Inorganic Chemistry, chemistry.chemical_compound, Oxalato, Magnetic properties, Antiferromagnetism, Molecule, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Génie des procédés, chemistry.chemical_classification, Coure, 010405 organic chemistry, Propietats magnètiques, Copper, 0104 chemical sciences, 3. Good health, Crystallography, Density functional calculations, chemistry, Ferromagnetism, Counterion, Monoclinic crystal system
Abstract

We report the preparation, crystal structure determination, magnetic properties and DFT calculations of five oxalato-bridged dicopper(II) complexes of formula [Cu-2(bpy)(2-)(H2O)(2)(C2O4)](CF3SO3)(2) (1), [Cu-2(bpy)(2)(C2O4)](PF6)(2) (2), [Cu-2(bpy)(2)(C2O4)](ClO4)(2) (3), [Cu-2(bpy)(2)Cl-2(C2O4)]center dot H2O (4) and [Cu-2(bpy)(2)(NO2)(2)(C2O4)] (5) (bpy = 2,2'-bipyridine and C2O42-= oxalate). Compounds 1, 2, 4 and 5 crystallize in the monoclinic system and 3 crystallizes in the triclinic system. The oxalate ligands in 1-5 adopt the bis-bidentate coordination mode and the two bpy molecules act as terminal ligands. The coordination of the counterions and the surroundings of the copper(II) ions differentiate the five compounds. The four nearest neighbours of copper(II) in 1-4 are roughly in the plane of the CuC2O4Cu framework, whereas they are in an almost perpendicular plane in 5. Using the isotropic Hamiltonian H = -JS(1)center dot S-2, where S-1 and S-2 are the spin quantum operators for Cu-1 and Cu-2; J is -384 cm(-1) for 1, -392 cm(-1) for 2 and -387 cm(-1) for 3, slightly decreasing to -328 cm(-1) for 4 and falling to -14 cm(-1) for 5. The influence of the anions on the magnetic properties of this family of compounds is explained by the changes in the overlap of the magnetic orbitals through the oxalate bridge. DFT calculations reproduce well the experimental values of J and provide an illustration of the magnetic orbitals.

Published
2018

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

Author

Lise-Marie Chamoreau, Geoffroy Guillemot, Teng Zhang, Anna Proust, Céline Paris, Louis Mazaud, Institut Parisien de Chimie Moléculaire (IPCM), Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de chimie moléculaire (LCM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-École polytechnique (X), De la Molécule aux Nanos-objets : Réactivité, Interactions et Spectroscopies (MONARIS), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Edifices PolyMétalliques (E-POM), Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS), Chimie Moléculaire de Paris Centre (FR 2769), Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-École normale supérieure - Paris (ENS Paris), and Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Titanium, 010405 organic chemistry, Chemistry, polyoxotungstate, chemistry.chemical_element, hydrogen peroxide, General Chemistry, Active surface, 010402 general chemistry, 01 natural sciences, Catalysis, 0104 chemical sciences, chemistry.chemical_compound, Silanol, Polymer chemistry, site-isolated catalysts, epoxidation, [CHIM]Chemical Sciences, Hydrogen peroxide, silanol, Tetrahydrofuran
Abstract

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

Published
2018

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