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2018



  • P. a Evenou, J. Rossignol, G. Pembouong, A. Gothland, D. Colesnic, R. Barbeyron, S. Rudiuk, A. - G. Marcelin, M. Ménand, D. Baigl, V. Calvez, L. Bouteiller, and M. Sollogoub, “Bridging beta-Cyclodextrin prevents self-inclusion and allows formation of supramolecular polymers: self-assembly and cooperative interaction with nucleic acids”, Angewandte Chemie International Edition, Apr. 2018.
    Tags: GOBS, POLE 3, POLE 4, POLYMERES.


  • L. Bacri, H. Mamad-Hemouch, C. Przybylski, B. Thiebot, G. Patriarche, N. Jarroux, and J. Pelta, “Biomimetic ion channels formation by emulsion based on chemically modified cyclodextrin nanotubes”, Faraday Discussions, 2018.

  • M. Ben Haddada, M. Salmain, and S. Boujday, “Gold colloid-nanostructured surfaces for enhanced piezoelectric immunosensing of staphylococcal enterotoxin A”, SENSORS AND ACTUATORS B-CHEMICAL, vol. 255, no. 2, p. 1604-1613, Mar. 2018.


  • L. Benda, B. Doistau, B. Hasenknopf, and G. Vives, “Synthesis and Guest Recognition of Switchable Pt-Salphen Based Molecular Tweezers”, Molecules, vol. 23, no. 5, p. 990, Apr. 2018.


  • N. Bridonneau, P. Quatremare, H. J. von Bardeleben, J. - L. Cantin, S. Pillet, E. - E. Bendeif, and V. Marvaud, “Direct Evidence of a Photoinduced Electron Transfer in Diluted “Molybdenum-Copper” Molecular Compounds”, European Journal of Inorganic Chemistry, vol. 2018, no. 3-4, p. 370-377, Jan. 2018.
    Abstract: For the first time, direct evidence of a photoinduced intramolecular electron transfer has been found in the “molybdenum-copper“ family of cyanide complexes that corresponds to a [MoIV–CuII]→[MoV–CuI] transition. The design and synthesis of a diluted molecular system, [Mo(Zn(1–x)Cux)2-tren] (x = 0, ε, 1, 5 and 10 %, , with ε corresponding to ppm ratio), viewed as new model compounds, have allowed good characterization of the metastable states involved in the process and provided evidence for two different mechanisms. By using squid magnetometry, EPR spectroscopy and X-ray diffraction, the results of this study have confirmed not only the photoinduced electron transfer, but also supports the light-induced excited spin state trapping effect centred on the molybdenum, thought to be due to the presence of a high-spin state (S = 1). This article provides a better understanding of the photomagnetic behaviour in Mo-Cu complexes and reveals the importance of orbital overlap to differentiate the two effects.
    Tags: Copper, E-POM, Electron transfer, Magentic properties, Molybdenum, Photomagnetism, POLE 2, Spin transition.
    Attachment Full Text PDF 1.7 Mb (source)


  • S. De, S. Tewary, D. Garnier, Y. Li, G. Gontard, L. Lisnard, A. Flambard, F. Breher, M. - L. Boillot, G. Rajaraman, and R. Lescouëzec, “Solution and Solid-State Study of the Spin-Crossover [FeII(R-bik)3](BF4)2 Complexes (R = Me, Et, Vinyl)”, European Journal of Inorganic Chemistry, vol. 2018, no. 3-4, p. 414-428, Jan. 2018.
    Abstract: The magnetic properties of three spin-crossover complexes, [FeII(R-bik)3](BF4)2·nH2O (1–3), based on bis(imidazolyl)ketone ligands, were investigated in solution and the solid state. Their properties were compared with those of the ketone-free analogue, [FeII(bim)3](OTf)2 (4). The alkyl and vinyl R groups have weak influence on the transition temperature, T1/2, in solution, while stronger differences are observed in the solid state, because different intermolecular interactions occur in 1–3. The spin-state equilibria in solution were followed by SQUID magnetometry and the Evans NMR spectroscopy method. Interestingly, the equilibria can also be simply and efficiently probed by following the temperature dependence of an adequately chosen 1H chemical shift. Overall, these experiments give coherent results, with T1/2 located between 320 and 335 K, a narrow range, in comparison with the solid state. DFT calculations have allowed the rationalization of the magnetic differences. The molecular-orbital and spin-density calculations reveal that the presence of the C=O group between the imidazolyl units in the ligands of 1–3 leads to an extended aromatic system, an effective π-acceptor effect, stabilizing the LS state and reducing the LS–HS gap, in comparison with 4.
    Tags: Density functional calculations, ERMMES, Iron, Paramagnetic NMR spectroscopy, POLE 2, Spin crossover, β-Diimine ligand.
    Attachment Full Text PDF 3.1 Mb (source)


  • S. Dhifaoui, C. Mchiri, P. Quatremare, V. Marvaud, A. Bujacz, and H. Nasri, “Molecular structure, magnetic properties, cyclic voltammetry of the low-spin iron(III) Bis(4-ethylaniline) complex with the para-chloro substituted meso-tetraphenylporphyrin”, Journal of Molecular Structure, vol. 1153, p. 353-359, Feb. 2018.
    Abstract: In this study, the preparation of a new iron(III) hexacoordinated metalloporphyrin namely the bis(4-ethylaniline){meso-tetra(para-chlorophenyl)porphyrinato}iron(III) triflate hemi-4-ethylaniline monohydrate with the formula [FeIII(TClPP)(PhEtNH2)2]SO3CF3•1/2PhEtNH2•H2O (I) was reported. This is the first example of an iron(III) metalloporphyrin bis(primary amine) with an aryl group adjacent to the amino group. This species was characterized by elemental, spectroscopic analysis including UV–visible and IR data, cyclic voltammetry, SQUID measurements and X-ray molecular structure. The mean equatorial distance between the iron(III) and the nitrogens of the porphyrin is appropriate for a low-spin (S = 1/2) iron(III) porphyrin complex. The magnetic data confirm the low-spin state of our ferric derivative while the cyclic voltammetry indicates a shift of the half potential E1/2[Fe(III)/Fe(II)] of complex (I) toward more negative value. In the crystal of (I), the [FeIII(TClPP)(PhEtNH2)2]+ ions, the triflate counterions and the water molecules are involved in a number of O__H⋯O, N__H⋯O, C–H⋯O and C__H⋯π intermolecular interactions forming a three-dimension network.
    Tags: E-POM, Iron(III) porphyrins, Magnetic data, POLE 2, UV–Visible, X-ray molecular structure.


  • S. Dhifaoui, S. Nasri, G. Gontard, A. C. Ghosh, Y. Garcia, C. Bonifàcio, S. Najmudin, V. Marvaud, and H. Nasri, “Synthesis, Mössbauer, cyclic voltammetry, magnetic properties and molecular structures of the low-spin iron(III) bis(pyrazine) complexes with the para-fluoro and para-chloro substituted meso-tetraphenylporphyrin”, Inorganica Chimica Acta, vol. 477, p. 114-121, May 2018.
    Abstract: Two new bis(pyrazine) iron(III) meso-porphyrin complexes are reported here: the bis(pyrazine)[5,10,15,20-tetra(para-fluoro-phenyl)porphyrinato]iron(III) triflate; [Fe(TFPP)(pyz)2]SO3CF3 (1) and the bis(pyrazine)[5,10,15,20-tetra(para-chlorophenyl)porphyrinato]iron(III) triflate; [Fe(TClPP)(pyz)2]SO3CF3 (2). The X-ray molecular structures of 1–2 show that the planes of the two pyrazine axial ligands are perpendicular and that the porphyrin macrocycles of these derivatives are very distorted, leading to a short average equatorial iron-pyrrole N atoms distance appropriate for low-spin ferric porphyrinates. The Mössbauer data of 1–2 feature relatively low values of the quadrupole splitting (ΔEQ ∼ 1.20 mm.s−1) appropriate for low-spin Fe(III) metalloporphyrin with perpendicular orientation of N-donor planar ligands. The temperature dependence of the magnetic susceptibility and the magnetization curves have shown that the results for complexes 1–2 confirm the low-spin state of our two-ferric species, while the cyclic voltammetry data show that the half potential [Fe(III)/Fe(II)] values are shifted anodically compared to the β-pyrrole substituted porphyrin octaethylporphyrin with parallel bis(N-donor) planar axial ligands.
    Tags: E-POM, Iron(III) porphyrins, Magnetic properties, Mössbauer, POLE 2, UV-visible, X-ray molecular structure.
  • B. Doistau, L. Benda, B. Hasenknopf, V. Marvaud, and G. Vives, “Switching Magnetic Properties by a Mechanical Motion”, Magnetochemistry, vol. 4, no. 1, p. 5, Jan. 2018.


  • J. Elloumi-Mseddi, S. Mnif, N. Akacha, B. Hakim, P. Pigeon, G. Jaouen, S. Top, and S. Aifa, “Selective cytotoxicity of arene tricarbonylchromium towards tumour cell lines”, Journal of Organometallic Chemistry, vol. 862, p. 7-12, 2018.
    Tags: 50% inhibitory concentration, CHEMBIO, Cytotoxicity, Inorganic chromium (VI), Organometallics, POLE 3, Tricarbonylchromium, Tumour cell lines.


  • L. Fensterbank, J. - P. Goddard, and C. Ollivier, “Visible-Light-Mediated Free Radical Synthesis”, in Visible Light Photocatalysis in Organic Chemistry, Wiley-Blackwell, 2018, p. 25-71.
    Abstract: This chapter concentrates on the photocatalytic generation of radical intermediates that have already been encountered in the past and generated through other pathways. It particularly emphasizes how photocatalysis can really improve the reaction conditions and outcomes. Different oxygenated moieties can be introduced by photocatalysis in place of an initial C—H bond. The development of visible-light photoredox catalysis for radical synthesis has demonstrated high efficiency, selectivity, versatility, and functional group tolerance in various transformations, becoming of great interest in cascade processes intramolecular radical steps. One of the most developed cascade sequence is tandem intermolecular radical addition/homolytic aromatic substitution, which first comprises radical addition onto activated double bond followed by cyclization onto arene and rearomatization by subsequent oxidation of the radical adduct. Radical multicomponent processes have emerged as a convenient and flexible strategy to elaborate complex molecular building blocks. Among them, visible-light photoredox catalysis proved to be efficient for promoting radical/cationic multicomponent reactions (MCRS).
    Tags: cationic multicomponent reaction, C—C bond formation, C—X bond formation, MACO, photocatalytic cycle, POLE 1, radical cascade applications, radical intermediates, radical multicomponent reaction, visible-light-mediated free radical synthesis.


  • F. Forato, A. Belhboub, J. Monot, M. Petit, R. Benoit, V. Sarou‐Kanian, F. Fayon, D. Jacquemin, C. Queffelec, and B. Bujoli, “Phosphonate-Mediated Immobilization of Rhodium/Bipyridine Hydrogenation Catalysts”, Chemistry – A European Journal, vol. 24, no. 10, p. 2457-2465, Feb. 2018.
    Abstract: RhL2 complexes of phosphonate-derivatized 2,2′-bipyridine (bpy) ligands L were immobilized on titanium oxide particles generated in situ. Depending on the structure of the bipy ligand—number of tethers (1 or 2) to which the phosphonate end groups are attached and their location on the 2,2′-bipyridine backbone (4,4′-, 5,5′-, or 6,6′-positions)—the resulting supported catalysts showed comparable chemoselectivity but different kinetics for the hydrogenation of 6-methyl-5-hepten-2-one under hydrogen pressure. Characterization of the six supported catalysts suggested that the intrinsic geometry of each of the phosphonate-derivatized 2,2′-bipyridines leads to supported catalysts with different microstructures and different arrangements of the RhL2 species at the surface of the solid, which thereby affect their reactivity.
    Tags: hydrogenation, immobilization, MACO, N ligands, POLE 1, rhodium, supported catalysts.
    Attachment Full Text PDF 1.1 Mb (source)


  • G. Gaiffe, M. C. Bridoux, C. Costanza, and R. B. Cole, “A systematic tandem mass spectrometric study of anion attachment for improved detection and acidity evaluation of nitrogen-rich energetic compounds”, Journal of Mass Spectrometry, vol. 53, no. 1, p. 21-29, 2018.


  • G. Gaiffe, R. B. Cole, S. Lacpatia, and M. C. Bridoux, “Characterization of Fluorinated Polymers by Atmospheric-Solid-Analysis-Probe High-Resolution Mass Spectrometry (ASAP/HRMS) Combined with Kendrick-Mass-Defect Analysis”, Analytical Chemistry, vol. 90, no. 10, p. 6035-6042, May 2018.


  • A. Gosset, Z. Xu, F. Maurel, L. - M. Chamoreau, S. Nowak, G. Vives, C. Perruchot, V. Heitz, and H. - P. Jacquot de Rouville, “A chemically-responsive bis-acridinium receptor”, New Journal of Chemistry, vol. 42, no. 6, p. 4728-4734, 2018.


  • B. Habchi, S. Alves, D. Jouan-Rimbaud Bouveresse, B. Appenzeller, A. Paris, D. N. Rutledge, and E. Rathahao-Paris, “Potential of dynamically harmonized Fourier transform ion cyclotron resonance cell for high-throughput metabolomics fingerprinting: control of data quality”, Analytical and Bioanalytical Chemistry, vol. 410, no. 2, p. 483-490, 2018.


  • B. Habchi, A. Kassouf, Y. Padellec, E. Rathahao-Paris, S. Alves, D. N. Rutledge, J. Maalouly, and V. Ducruet, “An untargeted evaluation of food contact materials by flow injection analysis-mass spectrometry (FIA-MS) combined with independent components analysis (ICA)”, Analytica Chimica Acta, 2018.


  • J. - R. Jiménez, A. Sugahara, M. Okubo, A. Yamada, L. - M. Chamoreau, L. Lisnard, and R. Lescouëzec, “A [FeIII(Tp)(CN)3]− scorpionate-based complex as a building block for designing ion storage hosts (Tp: hydrotrispyrazolylborate)”, Chemical Communications, Apr. 2018.
    Abstract: Using a scorpionate-based complex, [FeIII(Tp)(CN)3]−, as a building block, a new cyanide-based molecular material [{FeIII(Tp)(CN)3}2NiII(H2O)2]·4H2O (1), which can be viewed as a lower dimensional model of Prussian blue analogues, was investigated as a lithium-ion storage host.
    Tags: ERMMES, POLE 2.
    Attachment Full Text PDF 1.7 Mb (source)


  • Y. Journaux, J. Ferrando-Soria, E. Pardo, R. Ruiz-Garcia, M. Julve, F. Lloret, J. Cano, Y. Li, L. Lisnard, P. Yu, H. Stumpf, and C. L. M. Pereira, “Design of Magnetic Coordination Polymers Built from Polyoxalamide Ligands: A Thirty Year Story”, European Journal of Inorganic Chemistry, vol. 2018, no. 3-4, p. 228-247, Jan. 2018.
    Abstract: The aim of this review is to pay tribute to the legacy of O. Kahn. Kahn's credo was to synthesize magnetic compounds with predictable structure and magnetic properties. This is illustrated herein with results obtained by Kahn's group during his Orsay period thirty years ago, but also on the basis of our recent results on the synthesis of coordination polymers with oxamate ligands. The first part of this review is devoted to a short description of the necessary knowledge in physics and theoretical chemistry that Kahn and his group have used to select oxamate ligands, the complex-as-ligand strategy and the synthesis of heterobimetallic systems. Then, we describe the strategies we have later used to obtain the desired target compounds. The use of complexes as building-blocks, associated to a control of the metal ions chirality and stoichiometry, allowed us to obtain coordination polymers with predictable dimensionality. For the synthesis of single-chain magnets (SCMs) we show that the ligand chemical flexibility makes the isolation of the chains in the solid and the occurence of slow magnetic relaxation possible. For 1D and 2D molecule-based magnets (MBMs), the magnetic ordering strongly depends on the interchain or interplane interactions, which are difficult to control. Again the flexibility of the oxamate ligands allowed their strengthening in the solid sate, yielding MBMs with critical temperatures up to 30 K. We will also present our results on 3D coordination polymers, particularly on the porous magnets displaying large octagonal channels. This family of porous MBMs possess outstanding chemical properties, such as post-synthetic transformation in the solid state. Finally, we will also show that oxamate ligands allows the design of multifunctional materials, as in the case of the first chiral SCM. Overall, the results presented in this review show the impressive potential the oxamate ligands have for the design of coordination polymers.
    Tags: Bridging ligands, Coordination Polymer, ERMMES, Heterometallic complexes, Ligand design, Magnetic properties, Metal-Organic Frameworks, Metallacycles, N, O ligands, POLE 2.
    Attachment Full Text PDF 8.5 Mb (source)


  • Y. Journaux, J. Ferrando-Soria, E. Pardo, R. Ruiz-Garcia, M. Julve, F. Lloret, J. Cano, Y. Li, L. Lisnard, P. Yu, H. Stumpf, and C. L. M. Pereira, “Design of Magnetic Coordination Polymers Built from Polyoxalamide Ligands: A Thirty Year Story”, Eur. J. Inorg. Chem., vol. 2018, no. 3-4, p. 228–247, Jan. 2018.
    Abstract: The aim of this review is to pay tribute to the legacy of O. Kahn. Kahn's credo was to synthesize magnetic compounds with predictable structure and magnetic properties. This is illustrated herein with results obtained by Kahn's group during his Orsay period thirty years ago, but also on the basis of our recent results on the synthesis of coordination polymers with oxamate ligands. The first part of this review is devoted to a short description of the necessary knowledge in physics and theoretical chemistry that Kahn and his group have used to select oxamate ligands, the complex-as-ligand strategy and the synthesis of heterobimetallic systems. Then, we describe the strategies we have later used to obtain the desired target compounds. The use of complexes as building-blocks, associated to a control of the metal ions chirality and stoichiometry, allowed us to obtain coordination polymers with predictable dimensionality. For the synthesis of single-chain magnets (SCMs) we show that the ligand chemical flexibility makes the isolation of the chains in the solid and the occurence of slow magnetic relaxation possible. For 1D and 2D molecule-based magnets (MBMs), the magnetic ordering strongly depends on the interchain or interplane interactions, which are difficult to control. Again the flexibility of the oxamate ligands allowed their strengthening in the solid sate, yielding MBMs with critical temperatures up to 30 K. We will also present our results on 3D coordination polymers, particularly on the porous magnets displaying large octagonal channels. This family of porous MBMs possess outstanding chemical properties, such as post-synthetic transformation in the solid state. Finally, we will also show that oxamate ligands allows the design of multifunctional materials, as in the case of the first chiral SCM. Overall, the results presented in this review show the impressive potential the oxamate ligands have for the design of coordination polymers.
    Tags: Bridging ligands, Coordination Polymer, ermmes, Heterometallic complexes, Ligand design, Magnetic properties, Metal-Organic Frameworks, Metallacycles, N, O ligands, POLE 2.


  • S. H. Kyne, M. Clémancey, G. Blondin, E. Derat, L. Fensterbank, A. Jutand, G. Lefèvre, and C. Ollivier, “Elucidating Dramatic Ligand Effects on SET Processes: Iron Hydride versus Iron Borohydride Catalyzed Reductive Radical Cyclization of Unsaturated Organic Halides”, Organometallics, vol. 37, no. 5, p. 761-771, Mar. 2018.
    Abstract: An iron(II) borohydride complex ([(η1-H3BH)FeCl(NCCH3)4]) is employed as the precatalyst in iron-catalyzed radical cyclizations of unsaturated organic halides in the presence of NaBH4. Mechanistic investigations have established that the ligand bound to the metal center (acetonitrile versus ethylenebis(diphenylphosphine) (dppe)) plays a crucial role in the structure and reactivity of the active anionic iron(I) hydride ([HFeCl(dppe)2]−) and borohydride ([(η1-H3BH)FeCl(NCCH3)4]−) with unsaturated haloacetals. This work provides new insights into iron(I) hydride and borohydride species and their potential implication in single-electron processes.
    Tags: MACO, POLE 1.


  • O. Makrygenni, E. Secret, A. Michel, D. Brouri, V. Dupuis, A. Proust, J. - M. Siaugue, and R. Villanneau, “Heteropolytungstate-decorated core-shell magnetic nanoparticles: A covalent strategy for polyoxometalate-based hybrid nanomaterials”, Journal of Colloid and Interface Science, vol. 514, p. 49-58, Mar. 2018.
    Abstract: Amino-functionalized core–shell magnetic nanoparticles have been covalently grafted with Polyoxometalates (POMs). These multifunctional nanocomposites have been obtained through the coupling of heteropolytungstate-based hybrids bearing carboxylic acid functions with aminopropyl functions that decorate the core–shell nanoparticles. The physical properties of the resulting materials have been studied by a large set of techniques. The very good nanostructuration of the POMs at the surface of the obtained nanoparticles have thus been directly observed by high-resolution transmission electronic microscopy (HR-TEM). Furthermore, the hyperthermia properties of these nanocomposites have been also considered as a function of the size of the magnetic core. Finally, the stability of these suspensions in organic media makes them particularly interesting in the frame of their processing or their potential use as nanocatalysts.
    Tags: Core-shell nanoparticles, E-POM, HR-TEM, Hybrid materials, POLE 2, Polyoxometalates.


  • F. Medici, G. Gontard, E. Derat, G. Lemière, and L. Fensterbank, “Synthesis of Stable Pentacoordinate Silicon(IV)–NHC Adducts: An Entry to Anionic N-Heterocyclic Carbene Ligands”, Organometallics, vol. 37, no. 4, p. 517-520, Feb. 2018.
    Abstract: This work features the previously undescribed interactions of Martin’s spirosilane with different types of N-heterocyclic carbenes (NHCs). The level of interaction proved to be strongly dependent on the size of the Lewis base and could vary from the formation of isolable classical Lewis adducts to abnormal Lewis adducts, as evidenced by X-ray diffraction structure analyses and NMR studies. It has been found that abnormal adducts could be used as precursors for the synthesis of anionic NHCs bearing a weakly coordinating siliconate component. Complexation of these new types of carbenes with gold(I) and copper(I) has been efficiently accomplished. DFT calculations performed on the siliconate-based anionic NHC ligands revealed a high-lying HOMO and therefore a strong σ-donor character.
    Tags: MACO, POLE 1.


  • M. Ménand, M. Sollogoub, B. Boitrel, and S. Le Gac, “Cyclodextrin-Sandwiched Hexaphyrin Hybrids: Side-to-Side Cavity Coupling Switched by a Temperature- and Redox-Responsive Central Device”, Chemistry - A European Journal, vol. 24, no. 22, p. 5804-5812, Apr. 2018.


  • F. Mercier-Bion, J. Li, H. Lotz, L. Tortech, D. Neff, and P. Dillmann, “Electrical properties of iron corrosion layers formed in anoxic environments at the nanometer scale”, Corrosion Science, vol. 137, p. 98-110, Jun. 2018.
    Abstract: The electrical properties of the corrosion layers on archaeological iron artefacts were determined by Conductive Atomic Force Microscopy. Different corrosion products were studied: FeII carbonates, magnetite entrapped in the carbonate, and iron sulfides. The results indicate that the ferrous carbonate matrix is insulating, and that magnetite and iron sulfides have a conductive character, although these phases are not systematically connected to the metal. This suggests that electrons produced by the anodic dissolution of metal would be conducted to the external part of the corrosion product layer through a three-dimensional network of connected magnetite strips passing through the ferrous carbonate matrix.
    Tags: Archaeological artefact, C-AFM, E-POM, Electrical properties, FESEM, Iron corrosion, POLE 2, μRaman.
  • R. K. Nandi, A. Perez‐Luna, D. Gori, R. Beaud, R. Guillot, C. Kouklovsky, V. Gandon, and G. Vincent, “Triflic Acid as an Efficient Brønsted Acid Promoter for the Umpolung of N‐Ac Indoles in Hydroarylation Reactions”, Advanced Synthesis & Catalysis, vol. 360, no. 1, p. 161-172, Jan. 2018.


  • T. Neva, T. Carmona, J. M. Benito, C. Przybylski, C. Ortiz Mellet, F. Mendicuti, and J. M. García Fernández, “Xylylene Clips for the Topology-Guided Control of the Inclusion and Self-Assembling Properties of Cyclodextrins”, The Journal of Organic Chemistry, vol. 83, no. 10, p. 5588-5597, May 2018.


  • C. Przybylski, J. M. Benito, V. Bonnet, C. O. Mellet, and J. M. García Fernández, “Revealing cooperative binding of polycationic cyclodextrins with DNA oligomers by capillary electrophoresis coupled to mass spectrometry”, Analytica Chimica Acta, vol. 1002, p. 70-81, 2018.


  • Y. Ren, K. Cheaib, J. Jacquet, H. Vezin, L. Fensterbank, M. Orio, S. Blanchard, and M. Desage‐El Murr, “Copper-Catalyzed Aziridination with Redox-Active Ligands: Molecular Spin Catalysis”, Chemistry – A European Journal, vol. 24, no. 20, p. 5086-5090, Apr. 2018.
    Abstract: Small-molecule catalysts as mimics of biological systems illustrate the chemists’ attempts at emulating the tantalizing abilities displayed by nature's metalloenzymes. Among these innate behaviors, spin multistate reactivity is used by biological systems as it offers thermodynamic leverage towards challenging chemical reactivity but this concept is difficult to translate into the realm of synthetic organometallic catalysis. Here, we report a rare example of molecular spin catalysis involving multistate reactivity in a small-molecule biomimetic copper catalyst applied to aziridination. This behavior is supported by spin state flexibility enabled by the redox-active ligand.
    Tags: aziridination, copper catalysis, E-POM, MACO, multistate reactivity, POLE 1, POLE 2, redox-active ligands, spin catalysis.
    Attachment Full Text PDF 963.4 kb (source)


  • S. Roland, J. Meijide Suarez, and M. Sollogoub, “Confinement of Metal-N-Heterocyclic Carbene Complexes to control reactivity in catalytic reactions”, Chemistry - A European Journal, Apr. 2018.


  • F. Roudesly, L. F. Veiros, J. Oble, and G. Poli, “Pd-Catalyzed Direct C–H Alkenylation and Allylation of Azine N-Oxides”, Organic Letters, vol. 20, no. 8, p. 2346-2350, Apr. 2018.
    Abstract: A Pd-catalyzed direct C2-alkenylation of azine N-oxides with allyl acetate is disclosed. The products are formed through an allylation/isomerization cascade process. The use of a tri-tert-butylphosphonium salt as the ligand precursor and KF is mandatory for optimal yields. When cinnamyl acetate is used, the same catalytic system promotes C2-cinnamylation of the azine N-oxide without subsequent isomerization. A mechanism is proposed on the basis of experimental studies and DFT calculations.
    Tags: POLE 1, ROCS.


  • Y. Tang, Z. - Y. Zhu, Y. Liu, H. Sun, Q. - Y. Song, and Y. Zhang, “The chemical structure and anti-aging bioactivity of an acid polysaccharide obtained from <i>rose</i> buds”, Food & Function, vol. 9, no. 4, p. 2300-2312, 2018.


  • Y. Tang, Z. - Y. Zhu, L. - C. Pan, H. Sun, Q. - Y. Song, and Y. Zhang, “Structure analysis and anti-fatigue activity of a polysaccharide from <i>Lepidium meyenii</i> Walp”, Natural Product Research, p. 1-10, Mar. 2018.


  • Y. Wang, P. M. Dansette, P. Pigeon, S. Top, M. J. McGlinchey, D. Mansuy, and G. Jaouen, “A new generation of ferrociphenols leads to a great diversity of reactive metabolites, and exhibits remarkable antiproliferative properties”, Chemical Science, p. -, 2018.


  • Y. Yang, Z. Wang, L. Zhang, B. Yin, L. Lv, J. He, Z. Chen, X. Wen, B. Qiao, W. Sun, M. Fang, and Y. Zhang, “Protective effect of gentiopicroside from Gentiana macrophylla Pall. in ethanol-induced gastric mucosal injury in mice”, Phytotherapy Research, vol. 32, no. 2, p. 259-266, 2018.


  • T. Zhang, L. Mazaud, L. - M. Chamoreau, C. Paris, A. Proust, and G. Guillemot, “Unveiling the Active Surface Sit

    es in Heterogeneous Titanium-Based Silicalite Epoxidation Catalysts: Input of Silanol-Functionalized Polyoxotungstates as Soluble Analogues”, ACS Catalysis, vol. 8, no. 3, p. 2330-2342, Mar. 2018.
    Abstract: We report on a site-isolated model for Ti(IV) by reacting [Ti(iPrO)4] with the silanol-functionalized polyoxotungstates [XW9O34–x(tBuSiOH)3]3– (X = P, x = 0, 1; X = Sb, x = 1, 2) in tetrahydrofuran. The resulting titanium(IV) complexes [XW9O34–x(tBuSiO)3Ti(OiPr)]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 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 H2O. In the case of 3, the hydrolysis reaction of the isopropoxide ligand is only little shifted toward the formation of a monomeric [PW9O34(tBuSiO)3Ti(OH)]3– (5) species [log K = −1.96], whereas 4 reacted readily with H2O to form a μ-oxo bridged dimer {[SbW9O33(tBuSiO)3Ti]2O}6– (6). The more confined was the coordination site, the more hydrophobic was 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-(η1-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 toward the formation of Ti(η2-O2) and H3O+ 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 [SbW9O33(tBuSiO)3Ti(OiPr)]3– (4), the evolution to Ti(η2-O2) 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 to assess the efficiency and integrity of 4 as precatalyst.
    Tags: E-POM, POLE 2.


  • C. Zheng, H. Qu, W. Liao, T. Bavaro, M. Terreni, M. Sollogoub, K. Ding, and Y. Zhang, “Chemoenzymatically synthesized GM3 analogues as potential therapeutic agents to recover nervous functionality after injury by inducing neurite outgrowth”, European Journal of Medicinal Chemistry, vol. 146, p. 613-620, 2018.


  • C. Zheng, M. Terreni, M. Sollogoub, and Y. Zhang, “Ganglioside GM3 and Its Role in Cancer”, Current Medicinal Chemistry, vol. 25, Jan. 2018.


  • X. Zhu, S. Xiao, D. Zhou, M. Sollogoub, and Y. Zhang, “Design, synthesis and biological evaluation of water-soluble per- O -methylated cyclodextrin-C 60 conjugates as anti-influenza virus agents”, European Journal of Medicinal Chemistry, vol. 146, p. 194-205, 2018.


  • Z. - Y. Zhu, L. - C. Pan, Y. Tang, and Y. Zhang, “Structural analysis and antioxidant activity of the glycoside from Imperial Chrysanthemum”, Bioorganic & Medicinal Chemistry Letters, vol. 28, no. 9, p. 1581-1590, 2018.

2017


  • P. a Zhang, C. Tugny, J. Meijide Suárez, M. Guitet, E. Derat, N. Vanthuyne, Y. M. Zhang, O. Bistri, V. Mouries-Mansuy, M. Ménand, S. Roland, L. Fensterbank, and M. Sollogoub, “Artificial chiral metallo-pockets including a single metal serving as both structural probe and catalytic center”, Chem, vol. 3, no. 1, p. 174-191, 2017.

  • P. a Zhang, C. Tugny, J. Meijide Suárez, M. Guitet, E. Derat, N. Vanthuyne, Y. M. Zhang, O. Bistri, V. Mouries-Mansuy, M. Ménand, S. Roland, L. Fensterbank, and M. Sollogoub, “Artificial chiral metallo-pockets including a single metal serving as both structural probe and catalytic center”, Chem, vol. 3, no. 1, p. 174-191, 2017.


  • P. a Zhang, J. Meijide Suárez, T. Driant, E. Derat, Y. Zhang, M. Ménand, S. Roland, and M. Sollogoub, “Cyclodextrin Cavity-Induced Mechanistic Switch in Copper-Catalyzed Hydroboration”, Angewandte Chemie International Edition, vol. 56, no. 36, p. 10821-10825.


  • F. Abbassi, M. Mbarek, D. Kreher, and K. Alimi, “Synthesis and characterization of a copolymer involving PVK and MEH-PPV for organic electronic devices”, Journal of Physics and Chemistry of Solids, vol. 103, p. 142-146.
    Abstract: A statistic copolymer denoted (PVK)x-(MEH-PPV)y containing poly(N-vinylcarbazole) (PVK) as well as poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV) building blocks was prepared by chemical oxidative way. Correlations structure-properties of the synthesized copolymer were investigated by using different experimental analyses (IR, XRD, ATG, optical absorption, PL and PLRT) combined with theoretical calculations (DFT). The new copolymer exhibits interesting properties compared to PVK and MEH-PPV homopolymers taken separately. The resulting copolymer has improved thermal stability and it exhibits original optical properties compared to the PVK and MEH-PPV ones as well as its reveled charge transfer process and the continuous donor acceptor existence. All these experimental and theoretical analysis argue the originality of this new material which could then be exploited in optoelectronics.
    Tags: A. Polymers, B. Chemical synthesis, C. Ab initio calculations, C. Optical properties, POLE 4, POLYMERES.


  • R. Albigès, P. Klein, S. Roi, F. Stoffelbach, C. Creton, L. Bouteiller, and J. Rieger, “Water-based acrylic coatings reinforced by PISA-derived fibers”, Polymer Chemistry.
    Abstract: Polymerization-induced self-assembly (PISA) is an efficient approach to synthesize self-assembled core–shell nanofibers in water, made of amphiphilic block copolymers. We demonstrate here for the first time that such anisotropic and high Tg nanofibers can be used as reinforcing fillers for water-based acrylic materials. This strategy opens the way for strong all-organic aqueous coatings.
    Tags: POLE 4, POLYMERES.
    Attachment Full Text PDF 407.3 kb (source)


  • Q. Arnoux, A. Boucly, V. Barth, R. Benbalagh, A. Cossaro, L. Floreano, M. Silly, F. Sirotti, E. Derat, S. Carniato, F. Bournel, J. - J. Gallet, D. Fichou, L. Tortech, and F. Rochet, “Energy-Level Alignment of a Hole-Transport Organic Layer and ITO: Toward Applications for Organic Electronic Devices”, ACS Applied Materials & Interfaces, vol. 9, no. 36, p. 30992-31004, Sep. 2017.
    Abstract: 2,2′,6,6′-Tetraphenyl-4,4′-dipyranylidene (DIPO-Ph4) was grown by vacuum deposition on an indium tin oxide (ITO) substrate. The films were characterized by atomic force microscopy as well as synchrotron radiation UV and X-ray photoelectron spectroscopy to gain an insight into the material growth and to better understand the electronic properties of the ITO/DIPO-Ph4 interface. To interpret our spectroscopic data, we consider the formation of cationic DIPO-Ph4 at the ITO interface owing to a charge transfer from the organic layer to the substrate. Ionization energy DFT calculations of the neutral and cationic species substantiate this hypothesis. Finally, we present the energetic diagram of the ITO/DIPO-Ph4 system, and we discuss the application of this interface in various technologically relevant systems, as a hole-injector in OLEDs or as a hole-collector interfacial layer adjacent to the prototypical OPV layer P3HT:PCBM.
    Tags: E-POM, POLE 1, POLE 2.


  • Q. Arnoux, B. Watts, S. Swaraj, F. Rochet, and L. Tortech, “X-ray microscopic investigation of molecular orientation in a hole carrier thin film for organic solar cells”, Nano Research, p. 1-12, Nov. 2017.
    Abstract: As dipyranylidenes are excellent hole carriers, applications in organic solar cells or organic light emitting diode are envisaged. In the present study, we investigate the morphology of 2,2′,6,6′-tetraphenyl-4,4′-dipyranylidene (DIPO-Ph4) deposited under vacuum on a silicon nitride (Si3N4) substrate, a paradigmatic system for the study of molecular crystal/inorganic substrate interfaces. Samples with various coating ratios and different thermal treatments were prepared. The films were characterized by atomic force microscopy and scanning transmission X-ray microscopy to gain insight into material growth. The results show a change in orientation at a molecular level depending upon the evaporation conditions. We are now able to tailor an organic layer with a specific molecular orientation and a specific electronic behavior.Open image in new window
    Tags: E-POM, POLE 2.
    Attachment Full Text PDF 2.2 Mb (source)


  • T. Auvray, M. - P. Santoni, B. Hasenknopf, and G. S. Hanan, “Covalent hybrids based on Re(I) tricarbonyl complexes and polypyridine-functionalized polyoxometalate: synthesis, characterization and electronic properties”, Dalton Transactions, vol. 46, no. 30, p. 10029-10036, 2017.


  • S. P. Babailov, E. V. Peresypkina, Y. Journaux, and K. E. Vostrikova, “Nickel(II) complex of a biradical: Structure, magnetic properties, high NMR temperature sensitivity and moderately fast molecular dynamics”, Sensors and Actuators B: Chemical, vol. 239, p. 405-412.


  • P. Barbier Saint Hilaire, A. Warnet, Y. Gimbert, U. M. Hohenester, G. Giorgi, M. - F. Olivier, F. Fenaille, B. Colsch, C. Junot, and J. - C. Tabet, “Mechanistic study of competitive releases of H2O, NH3 and CO2 from deprotonated aspartic and glutamic acids: Role of conformation”, Journal of Chromatography B, vol. 1047, p. 64-74.
    Abstract: The aims of this study were to highlight the impact of minor structural differences (e.g. an aminoacid side chain enlargement by one methylene group), on ion dissociation under collision-induced dissociation conditions, and to determine the underlying chemical mechanisms. Therefore, we compared fragmentations of deprotonated aspartic and glutamic acids generated in negative electrospray ionization. Energy-resolved mass spectrometry breakdown curves were recorded and MS3 experiments performed on an Orbitrap Fusion for high-resolution and high-mass accuracy measurements. Activated fragmentations were performed using both the resonant and non-resonant excitation modes (i.e., CID and HCD, respectively) in order to get complementary information on the competitive and consecutive dissociative pathways. These experiments showed a specific loss of ammonia from the activated aspartate but not from the activated glutamate. We mainly focused on this specific observed loss from aspartate. Two different mechanisms based on intramolecular reactions (similar to those occurring in organic chemistry) were proposed, such as intramolecular elimination (i.e. Ei-like) and nucleophilic substitution (i.e. SNi-like) reactions, respectively, yielding anions as fumarate and α lactone from a particular conformation with the lowest steric hindrance (i.e. with antiperiplanar carboxyl groups). The detected deaminated aspartate anion can then release CO2 as observed in the MS3 experimental spectra. However, quantum calculations did not indicate the formation of such a deaminated aspartate product ion without loss of carbon dioxide. Actually, calculations displayed the double neutral (NH3+CO2) loss as a concomitant pathway (from a particular conformation) with relative high activation energy instead of a consecutive process. This disagreement is apparent since the concomitant pathway may be changed into consecutive dissociations according to the collision energy i.e., at higher collision energy and at lower excitation conditions, respectively. The latter takes place by stabilization of the deaminated aspartate solvated with two residual molecules of water (present in the collision cell). This desolvated anion formed is an α lactone substituted by a methylene carboxylate group. The vibrational excitation acquired by [(D−H)−NH3]−during its isolation is enough to allow its prompt decarboxylation with a barrier lower than 8.4 kJ/mol. In addition, study of glutamic acid-like diastereomers constituted by a cyclopropane, hindering any side chain rotation, confirms the impact of the three-dimensional geometry on fragmentation pathways. A significant specific loss of water is only observed for one of these diastereomers. Other experiments, such as stable isotope labeling, need to be performed to elucidate all the observed losses from activated aspartate and glutamate anions. These first mechanistic interpretations enhance understanding of this dissociative pathway and underline the necessity of studying fragmentation of a large number of various compounds to implement properly new algorithms for de novo elucidation of unknown metabolites.
    Tags: CSOB, Electrospray high-resolution mass spectrometry, POLE 3, Regioselective dissociation, Unexpected cleavage of aspartate anion.

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