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Accueil > Les équipes > Architectures Moléculaires (A.R.C) > Publications

Publications

publié le , mis à jour le

2016



  • J. Dubarle-Offner, J. Moussa, H. Amouri, B. Jouvelet, L. Bouteiller, et M. Raynal, « Induced Circular Dichroism in Phosphine Gold(I) Aryl Acetylide Urea Complexes through Hydrogen-Bonded Chiral Co-Assemblies », Chemistry – A European Journal, vol. 22, nᵒ 12, p. 3985-3990.
    Résumé : Phosphine gold(I) aryl acetylide complexes equipped with a central bis(urea) moiety form 1D hydrogen-bonded polymeric assemblies in solution that do not display any optical activity. Chiral co-assemblies are formed by simple addition of an enantiopure (metal-free) complementary monomer. Although exhibiting an intrinsically achiral linear geometry, the gold(I) aryl acetylide fragment is located in the chiral environment displayed by the hydrogen-bonded co-assemblies, as demonstrated by induced circular dichroism (ICD).
    Mots-clés : ARC, gold complexes, induced circular dichroism, POLE 1, POLE 4, POLYMERES, sergeants and soldiers, supramolecular chirality, supramolecular polymers.


  • F. Jaroschik, A. Simonneau, G. Lemière, K. Cariou, N. Agenet, H. Amouri, C. Aubert, J. - P. Goddard, D. Lesage, M. Malacria, Y. Gimbert, V. Gandon, et L. Fensterbank, « Assessing Ligand and Counterion Effects in the Noble Metal Catalyzed Cycloisomerization Reactions of 1,6-Allenynes: a Combined Experimental and Theoretical Approach », ACS Catalysis, vol. 6, nᵒ 8, p. 5146-5160.
    Résumé : 1,6-Allenynes are useful mechanistic probes in noble-metal catalysis, since they can give rise to very distinct products in a highly selective fashion. Various cycloisomerization reactions have been described, and discrete mechanisms have been postulated. Of particular interest, whereas Alder-ene types of products can be obtained in a variety of ways using noble-metal catalysts (Au, Pt, Rh, ...), hydrindienes have been reported solely with gold and platinum under specific conditions. It was shown in a previous study that this intriguing transformation required the presence of chloride ligands at the active catalytic species. Herein, the factors governing the fate of 1,6-allenynes under cycloisomerization conditions have been studied more thoroughly, revealing a much more complex scenario. The nature of ligands, counterions, and metals was examined, showing that hydrindienes can be isolated in the absence of halides, using electron-rich, bulky triorganophosphines or carbene ligands. This crucial finding could also be used to access hydrindienes in high yields, not only with gold or platinum but also with silver. On the basis of mass spectrometry, NMR spectroscopy, and computations, refined mechanistic scenarios have been put forward, also rationalizing counterion effects. Notably, a metal vinylidene intermediate has been proposed for the formation of the hydrindiene derivatives. Finally, in the presence of tris((triphenylphosphine)gold)oxonium tetrafluoroborate as catalyst, a new pathway has been unveiled, involving gold alkyne σ,π complexes and leading to previously unobserved [2 + 2] cycloaddition compounds.
    Mots-clés : ARC, CSOB, MACO, POLE 1, POLE 2, POLE 3.


  • P. - H. Lanoë, J. Chan, G. Gontard, F. Monti, N. Armaroli, A. Barbieri, et H. Amouri, « Deep-Red Phosphorescent Iridium(III) Complexes with Chromophoric N-Heterocyclic Carbene Ligands: Design, Photophysical Properties, and DFT Calculations (Eur. J. Inorg. Chem. 11/2016) », European Journal of Inorganic Chemistry, vol. 2016, nᵒ 11, p. n/a-n/a.
    Mots-clés : ARC, Carbene ligands, Charge transfer, Iridium, luminescence, Photophysics, POLE 1.


  • J. Moussa, L. M. Chamoreau, M. P. Gullo, A. D. Esposti, A. Barbieri, et H. Amouri, « Induced phosphorescence from Pt → Ag and Ag(I)⋯Ag(I) metallophilic interactions in benzenedithiolatodiimine-Pt2/Ag2 clusters: a combined experimental and theoretical investigation », Dalton Transactions, vol. 45, nᵒ 7, p. 2906-2913.
    Résumé : We report the synthesis and luminescence properties of a novel platinum(II)–silver(I) cluster exhibiting supramolecular donor–acceptor dative Pt → Ag bonds as well as d10⋯d10 argentophilic interactions. This compound was obtained by a self-assembly process upon mixing silver triflate with the [Pt(bdt)(bpy)] (1) building block. The new compound was characterized by infrared, NMR (1H, 13C) and UV-vis spectroscopy. In addition, the molecular structure was unequivocally ascertained by a single-crystal X-ray diffraction study and shows that the assembly is identified as [(Pt2Ag2(o-bdt)2(bpy)2](CF3SO3)2 (2). Remarkably, the structure shows that complex 2 exists as two isomers I and II displaying different types of argentophilic interactions Ag⋯Ag as well as Pt → Ag dative bonds. These interactions are highly important and turn on phosphorescent emissions at low temperature depending on the nature of the isomer. The photophysical properties of both isomers were investigated and rationalized through TD-DFT calculations. This work paves the way to the synthesis of novel supramolecular assemblies displaying peculiar properties imparted from metallophilic as well as donor–acceptor metal–metal interactions.
    Mots-clés : ARC, POLE 1.


  • J. Moussa, G. R. Freeman, J. A. G. Williams, L. - M. Chamoreau, P. Herson, et H. Amouri, « Synthesis and Luminescence Properties of Cycloplatinated Complexes with a Chelating N∧C Pyridine-Derived N-Heterocyclic Carbene – Influence of 2,4,6-Triphenyl­phosphinine versus Triphenylphosphine », European Journal of Inorganic Chemistry, vol. 2016, nᵒ 5, p. 761-767.
    Résumé : Two cycloplatinated complexes of the form [Pt(NC)CH3(P)]+ incorporating a rare, bidentate NC-chelating pyridylpyridylidene ligand are reported. The phosphorus-based ligand P is either 2,4,6-triphenylphosphinine or triphenylphosphine. These mononuclear complexes have been fully characterised in solution and by single-crystal X-ray diffraction analysis. UV/Vis absorption and photoluminescence spectroscopy studies reveal strong phosphorescence from the phosphinine compound at 77 K but no emission from its triphenylphosphine analogue. This contrasting behaviour can be traced to the π-acceptor ability of the phosphabenzene ring, as corroborated by electrochemical and time-dependent DFT (TD-DFT) calculations.
    Mots-clés : ARC, Carbene ligands, luminescence, N li­gands, Phosphinines, Platinum, POLE 1.


  • J. Moussa, K. Haddouche, L. - M. Chamoreau, H. Amouri, et J. A. G. Williams, « New N^C^N-coordinated Pd(II) and Pt(II) complexes of a tridentate N-heterocyclic carbene ligand featuring a 6-membered central ring: synthesis, structures and luminescence », Dalton Transactions, vol. 45, nᵒ 32, p. 12644-12648.
    Résumé : We describe Pd(II) and Pt(II) complexes of an N^C^N-coordinating pincer-like ligand featuring two lateral pyridine rings and a 6-membered carbene core. Their crystal structures display 1-dimensional chains with short π–π and M(II)⋯M(II) interactions. Such interactions also impact on the photophysical properties, with the Pt(II) complex being luminescent in the solid state at room temperature.
    Mots-clés : ARC, POLE 1.


  • H. Sesolis, J. Dubarle-Offner, C. K. M. Chan, E. Puig, G. Gontard, P. Winter, A. L. Cooksy, V. W. W. Yam, et H. Amouri, « Highly Phosphorescent Crystals of Square-Planar Platinum Complexes with Chiral Organometallic Linkers: Homochiral versus Heterochiral Arrangements, Induced Circular Dichroism, and TD-DFT Calculations », Chemistry – A European Journal, vol. 22, nᵒ 24, p. 8032-8037.
    Résumé : A novel class of chiral luminescent square-planar platinum complexes with a π-bonded chiral thioquinonoid ligand is described. Remarkably the presence of this chiral organometallic ligand controls the aggregation of this square planar luminophor and imposes a homo- or hetero-chiral arrangement at the supramolecular level, displaying non-covalent Pt–Pt and π–π interactions. Interestingly these complexes are highly luminescent in the crystalline state and their photophysical properties can be traced to their aggregation in the solid state. A TD-DFT calculation is obtained to rationalize this unique behavior.
    Mots-clés : ARC, molecular aggregation, noncovalent interactions, photophysical properties, Platinum, POLE 1, supramolecular chirality.

2015



  • M. Gruselle, « Apatites: A new family of catalysts in organic synthesis », Journal of Organometallic Chemistry, vol. Complete, nᵒ 793, p. 93-101.
    Résumé : The development of green and sustainable chemistry is one of the most exciting challenges in modern chemistry. In this way, design of new catalysts for heterogeneous processes is of prime importance and plays a key role to reduce the impact of chemistry on the environment.Our approach to green chemistry deals with the use of an inexpensive suitable and recyclable material namely the apatite's family. Apatites, in which the composition and surface properties can be tuned, are themselves catalysts or can be used as support for catalytic centres in many organic reactions. In this review, we describe the state of the art in this emerging field.
    Mots-clés : ARC, POLE 1.

  • H. Sesolis, J. Moussa, G. Gontard, A. Jutand, M. P. Gullo, A. Barbieri, et H. Amouri, « A unique class of neutral cyclometalated platinum(II) complexes with pi-bonded benzenedithiolate: synthesis, molecular structures and tuning of luminescence properties », Dalton Transactions, vol. 44, nᵒ 7, p. 2973-2977.
    Résumé : A unique class of neutral cyclometalated platinum(II) complexes 2-4 with pi-bonded benzenedithiolate are reported including two X-ray molecular structures. To the best of our knowledge these are the first structures to be reported for cyclometalated platinum complexes with a benzenedithiolate ligand. All of the complexes are luminescent in fluid solution at room temperature and in frozen solvent glasses at 77 K and their emission properties can be tuned through ligand variation.
    Mots-clés : ARC, crystal-structure, dithiolate complexes, dithiooxamide complexes, excited-state properties, heteroleptic complexes, organometallic quinonoid linkers, oxidative addition, photophysical properties, POLE 1, pt(ii) complexes, terpyridyl complexes.

  • J. - P. Tranchier, J. Dubarle-Offner, L. Peyroux, G. Gontard, T. Riedel, P. J. Dyson, et H. Amouri, « Iridium-Stabilized pi-Selenocyclohexadienyls: Synthesis, Molecular Structure, and Cytotoxicity », Synlett, vol. 26, nᵒ 11, p. 1563-1566.
    Résumé : A series of iridium-stabilized selenocyclohexadienyls of general formula [Cp*Ir((5)-C6H5-nMenSe)][BF4] {Cp* = (5)-C5Me5, n = 0, n = 1, and n = 3} is described, with the selenocyclohexadienyl unit being isolated for the first time by -coordination to a Cp*Ir moiety. The solid-state structure of one of [Cp*Ir((5)-C6H2Me3Se)][BF4] was determined by single-crystal X-ray diffraction analysis. These compounds are obtained in good yields as orange-red microcrystalline solids by halogen displacement from the related -bonded arene-chlorinated starting materials using Na2Se as the selenium source. Furthermore, these new compounds display relevant cytotoxic properties towards human ovarian cancer cells.
    Mots-clés : activation, anticancer activity, ARC, behavior, cp-asterisk-ir, crystal-structure, iridium-stabilized intermediates, metals, phenols, pi-complexes, POLE 1, quinone methide complexes, reactivity, regioselective ortho-functionalization, selenocyclohexadienyls, X-ray crystal structure.

2014



  • A. Damas, H. Sesolis, M. N. Rager, L. M. Chamoreau, M. P. Gullo, A. Barbieri, et H. Amouri, « Ester-substituted cyclometallated rhodium and iridium coordination assemblies with π-bonded dioxolene ligand: synthesis, structures and luminescent properties », RSC Advances, vol. 4, nᵒ 45, p. 23740.
    Mots-clés : ARC, bonding properties, charge-distribution, electrochemical-behavior, heteroleptic complexes, organometallic quinonoid linkers, POLE 1, ray molecular-structure, resonance raman, ruthenium complexes, transition-metal-complexes, trisphat anion.
    Pièce jointe


  • C. Desmarets, T. Ducarre, M. Rager, G. Gontard, et H. Amouri, « Self-Assembled M2L4 Nanocapsules: Synthesis, Structure and Host-Guest Recognition Toward Square Planar Metal Complexes », Materials, vol. 7, nᵒ 1, p. 287-301.
    Mots-clés : ARC, chemistry, coordination cage, discrete, Encapsulation, host-guest, Palladium, POLE 1, principles, rational design, Self-assembly, serendipity, tetrafluoroborate anion, tetragonal cages, water.
    Pièce jointe


  • C. Desmarets, G. Gontard, A. L. Cooksy, M. N. Rager, et H. Amouri, « Encapsulation of a Metal Complex within a Self-Assembled Nanocage: Synergy Effects, Molecular Structures, and Density Functional Theory Calculations », Inorganic Chemistry, vol. 53, nᵒ 9, p. 4287-4294.
    Mots-clés : ARC, architectures, chiral recognition, coordination cage, crystal-structures, design, drug-delivery, organometallic cages, photosensitizers, POLE 1, supramolecular triangular hosts, tetrafluoroborate anion.
    Pièce jointe


  • J. Dubarle-Offner, C. M. Clavel, G. Gontard, P. J. Dyson, et H. Amouri, « Selenoquinones Stabilized by Ruthenium(II) Arene Complexes: Synthesis, Structure, and Cytotoxicity », Chemistry A European Journal, vol. 20, nᵒ 19, p. 5795-5801.
    Mots-clés : (eta(5)-pentamethylcyclopentadienyl)ruthenium pi-complexes, anticancer complexes, ARC, coordination, crystal-structure, cytotoxicity, in-vitro, Ligands, nucleophilic-substitution, Pi interactions, POLE 1, quinone methide complexes, ray molecular-structure, reactivity, Ruthenium, Sandwich complexes, selenoquinones.
    Pièce jointe

  • B. Maaten, J. Moussa, C. Desmarets, P. Gredin, P. Beaunier, T. Kanger, K. Toinsuaadu, D. Villemin, et M. Gruselle, « Cu-modified hydroxy-apatite as catalyst for Glaser-Hay C-C homo- coupling reaction of terminal alkynes », Journal of Molecular Catalysis a-Chemical, vol. 393, p. 112-116.
    Résumé : The oxidative Glaser-Hay coupling reaction of terminal alkynes is a very important reaction in organic chemistry to achieve the synthesis of diyne compounds. In general the reaction is performed under homogeneous conditions using Cu(I) or Cu(II) salts in the presence of a reagent such as tetramethylethylenediamine (TMEDA), which can bind to copper ions, an organic base and dioxygen. Although this reaction is known for a longtime, the mechanism is still under discussion. Pursuing our investigations on the use of apatites as catalysts for organic reactions we highlight in this work how it is possible to catalyze the Glaser-Hay reaction under heterogeneous conditions using a Cu-modified hydroxyapatite (Cu-HAp). With several para-substituted phenyl-acetylenes and alkynols we show that Cu-HAp acts as catalyst for C-C coupling reactions leading to diyne derivatives in high yields without using auxiliary chelating molecules and organic bases. These heterogeneous conditions allow an easy recovery of the catalyst and simplify the purification work-up. (C) 2014 Elsevier B.V. All rights reserved.
    Mots-clés : acetylenes, alkynes, Apatites, ARC, Calcium, carbonate, Copper, efficient, Glaser-Hay reaction, heterocycles, n-arylation, POLE 1, ru-hydroxyapatite, Ruthenium, water.

  • J. Moussa, L. M. Chamoreau, et H. Amouri, « Gold(I) complexes with a phosphinine ligand: synthesis and structur

    al characterization », Rsc Advances, vol. 4, nᵒ 23, p. 11539-11542.
    Résumé : The synthesis of two novel gold(I) complexes with a phosphinine ligand is reported. Reaction of a monodentate phosphinine ligand, 2,6-diphenyl-4-methylphosphorin (L-p; 1), with gold(I) molecular bricks leads to the preparation of two new mononuclear complexes with the general formulae [AuCl(L-p)] (2) and [Au(L-p)2](OTf) (3). The new compounds were spectroscopically characterized by infrared and NMR (H-1, C-13 and P-31). In addition, the molecular structure of [AuCl(L-p)] (2) was unequivocally ascertained by a single-crystal X-ray diffraction study. Furthermore the UV-Vis absorption and emission properties of these compounds were investigated. These complexes pave the way for the synthesis of a new class of phosphinine gold complexes displaying peculiar properties, which might hold promise as luminescent materials.
    Mots-clés : agents, alkynes, ARC, Catalysis, Coordination chemistry, design, luminescence, metal centers, perspectives, POLE 1, ray crystal-structures, reactivity.


  • J. Moussa, L. - M. Chamoreau, A. Degli Esposti, M. P. Gullo, A. Barbieri, et H. Amouri, « Tuning Excited States of Bipyridyl Platinum(II) Chromophores with π-Bonded Catecholate Organometallic Ligands: Synthesis, Structures, TD-DFT Calculations, and Photophysical Properties », Inorganic Chemistry, vol. 53, nᵒ 13, p. 6624-6633.
    Mots-clés : ARC, crystal-structures, density-functional theory, diimine complexes, electronic-structure, excitation-energies, heteroleptic complexes, luminescence properties, pbe0 model, POLE 1, quinonoid linkers, trisphat anion.
    Pièce jointe


  • J. Moussa, T. Cheminel, G. R. Freeman, L. - M. Chamoreau, J. A. G. Williams, et H. Amouri, « An unprecedented cyclometallated platinum(ii) complex incorporating a phosphinine co-ligand: synthesis and photoluminescence behaviour », Dalton Transactions, vol. 43, nᵒ 22, p. 8162.
    Mots-clés : activation, ARC, Coordination chemistry, exciton, homogeneous catalysis, Palladium, perspectives, phosphorescence, photophysical properties, POLE 1, reactivity, structural-characterization.
    Pièce jointe

2013



  • M. Augé, M. Barbazanges, A. T. Tran, A. Simonneau, P. Elley, H. Amouri, C. Aubert, L. Fensterbank, V. Gandon, M. Malacria, J. Moussa, et C. Ollivier, « Atroposelective [2+2+2] cycloadditions catalyzed by a rhodium(i)–chiral phosphate system », Chemical Communications, vol. 49, nᵒ 71, p. 7833.


  • A. Damas, L. - M. Chamoreau, A. L. Cooksy, A. Jutand, et H. Amouri, « π-Bonded Dithiolene Complexes: Synthesis, Molecular Structures, Electrochemical Behavior, and Density Functional Theory Calculations », Inorganic Chemistry, vol. 52, nᵒ 3, p. 1409-1417.
    Résumé : The synthesis and X-ray molecular structure of the first metal-stabilized o-dithiobenzoquinone [Cp*Ir-o-(?4-C6H4S2)] (2) are described. The presence of the metal stabilizes this elusive intermediate by π coordination and increases the nucleophilic character of the sulfur atoms. Indeed, the π-bonded dithiolene complex 2 was found to react with the organometallic solvated species [Cp*M(acetone)3][OTf]2 (M = Rh, Ir) to give a unique class of binuclear dithiolene compounds [Cp*Ir(C6H4S2)MCp*][OTf]2 [M = Rh (3), Ir (4)] in which the elusive dithiolene ?-C6H4S2 acts as a bridging ligand toward the two Cp*M moieties. The electrochemical behavior of all complexes was investigated and provided us with valuable information about their redox properties. Density functional theory (DFT) calculations on the π-bonded dithiobenzoquinone ligand and related bimetallic systems show that the presence of Cp*M at the arene system of the dithiolene ligand increases the stability compared to the known monomeric species [Cp*Ir-o-(C6H4S2-?2-S,S)] and enables these complexes Cp*Ir(C6H4S2)MCp*][OTf]2 (3 and 4) to act as electron reservoirs. Time-dependent DFT calculations also predict the qualitative trends in the experimental UV?vis spectra and indicate that the strongest transitions arise from ligand?metal charge transfer involving primarily the HOMO?1 and LUMO. All of these compounds were fully characterized and identified by single-crystal X-ray crystallography. These results illustrate the first examples describing the coordination chemistry of the elusive o-dithiobenzoquinone to yield bimetallic complexes with an o-benzodithiolene ligand. These compounds might have important applications in the area of molecular materials.
    Mots-clés : ARC, POLE 1.

  • A. Damas, M. P. Gullo, M. N. Rager, A. Jutand, A. Barbieri, et H. Amouri, « Near-infrared room temperature emission from a novel class of Ru(II) heteroleptic complexes with quinonoid organometallic linker », Chemical Communications, vol. 49, nᵒ 36, p. 3796-3798.
    Résumé : A novel class of luminescent octahedral ruthenium complexes 2-4 displaying a pi-bonded quinonoid ligand is described. Remarkably, the presence of this organometallic ligand affects their UV-vis properties and transforms them into panchromatic absorbers. Furthermore, it turns on room temperature NIR emissions.
    Mots-clés : absorption-spectra, ARC, design, electrochemical-behavior, luminescence properties, octahedral bimetallic assemblies, photophysical properties, POLE 1, polypyridine complexes, ray molecular-structure, Ruthenium, transition-metal-complexes.


  • R. Djeda, C. Desmarets, L. - M. Chamoreau, Y. Li, Y. Journaux, G. Gontard, et H. Amouri, « Meso-Helicates with Rigid Angular Tetradentate Ligand: Design, Molecular Structures, and Progress Towards Self-Assembly of Metal–Organic Nanotubes », Inorganic Chemistry, vol. 52, nᵒ 22, p. 13042-13047.


  • J. Dubarle-Offner, M. Barbazanges, M. Augé, C. Desmarets, J. Moussa, M. R. Axet, C. Ollivier, C. Aubert, L. Fensterbank, V. Gandon, M. Malacria, G. Gontard, et H. Amouri, « Gold Compounds Anchored to a Metalated Arene Scaffold: Synthesis, X-ray Molecular Structures, and Cycloisomerization of Enyne », Organometallics, vol. 32, nᵒ 6, p. 1665-1673.
    Résumé : A novel series of π-complexes of phosphino ligands, [Cp*Ru(?6-arene-PAr2)][OTf], has been prepared in which the diarylphosphine unit is attached to a metalated π-arene scaffold. These organometallic phosphino ligands display either an electron-donating methyl group (?PAr2 = ?P(p-tol)2) or electron-withdrawing trifluoromethyl group (?PAr2 = ?P(p-C6H4CF3)2). This unique class of metallo ligands was converted to heterodinuclear gold complexes upon treatment with [AuCl(tht)]. The molecular structures of [Cp*Ru(?6-p-CH3C6H4-P(p-tol)2-Au-Cl)][OTf] and [Cp*Ru(?6-C6H5-P(p-C6H4CF3)2)-Au-Cl][OTf] were ascertained by single-crystal X-ray diffraction. A comparative study of these structures with that of [Cp*Ru(?6-C6H5-PPh2-Au-Cl)][OTf] previously reported revealed important information about the electronic nature of the gold center when it is bonded to a ?PPh2, ?P(p-tol)2, or ?P(p-C6H4CF3)2 metallo ligand. DFT computations also shed light on the effect of [Cp*Ru+] coordination to [AuCl(PAr3)] precatalysts. Several complexes of the family with electron-donating and -withdrawing groups were evaluated toward cycloisomerization reactions of a classical N-tethered 1,6-enyne. These results are presented and discussed.
    Mots-clés : ARC, COS, MACO, POLE 1.


  • M. Gruselle, Y. Li, N. Ovanesyan, V. Makhaev, G. Shilov, F. Mushenok, C. Train, et S. Aldoshin, « (S)-(−)-(2-MeBu)N(Pr)2MeI Salt as Template in the Enantioselective Synthesis of the Enantiopure Two-dimensional (S)-(−)-(2-MeBu)N(Pr)2Me[ΛMnΔCr(C2O4)3] Ferromagnet », Chirality, vol. 25, nᵒ 8, p. 444–448.
    Résumé : We describe herein the synthesis of (rac)- or enantiopure (S)-(−)-(2-MeBu)N(Pr)2MeI ammonium salts. These racemic and enantiopure ammonium salts were used as cationic templates to obtain new two-dimensional (2D) ferromagnets [(rac)-(2-MeBu)N(Pr)2Me][MnCr(C2O4)3] and [(S)-(−)-(2-MeBu)N(Pr)2Me][ΔMnΛ nCr(C2O4)3]. The absolute configuration of the hexacoordinated Cr(III) metallic ion in the enantiopure 2D network was determined by a circular dichroism measurement. The structure of [(2-MeBu)N(Pr)2Me][MnCr(C2O4)3], established by single crystal X-ray diffraction, belongs to the chiral P63 space group. According to direct current (dc) magnetic measurements, these compounds are ferrromagnets with a temperature Tc = 6°K. Chirality 25:444–448, 2013. © 2013 Wiley Periodicals, Inc.
    Mots-clés : 2D chiral networks, ammonium salts, ARC, ERMMES, ferromagnets, MMMAX, POLE 1, POLE 2.


  • B. Matt, J. Fize, J. Moussa, H. Amouri, A. Pereira, V. Artero, G. Izzet, et A. Proust, « Charge photo-accumulation and photocatalytic hydrogen evolution under visible light at an iridium(iii)-photosensitized polyoxotungstate », Energy & Environmental Science, vol. 6, nᵒ 5, p. 1504.


  • B. Matt, X. Xiang, A. L. Kaledin, N. Han, J. Moussa, H. Amouri, S. Alves, C. L. Hill, T. Lian, D. G. Musaev, G. Izzet, et A. Proust, « Long lived charge separation in iridium(III)-photosensitized polyoxometalates: synthesis, photophysical and computational studies of organometallic–redox tunable oxide assemblies », Chemical Science, vol. 4, nᵒ 4, p. 1737-1745.
    Résumé : Keggin and Dawson-type polyoxometalates (POMs) covalently grafted to heteroleptic cyclometalated iridium(iii) complexes (POM–[Ir] dyads) have been prepared by postfunctionalization of organosilyl and organotin POM derivatives. Electronic properties of these 4 photosensitized POM–[Ir] dyads were evaluated by
    Mots-clés : ARC, CSOB, E-POM, POLE 1, POLE 2, POLE 3, POM.


  • J. Moussa, L. M. Chamoreau, et H. Amouri, « Planar Chiral Iridium Complexes with the Δ-TRISPHAT Anion: Toward the First Enantiopure o-Quinone Methide π-Complex », Chirality, vol. 25, nᵒ 8, p. 449–454.
    Résumé : We describe the resolution of a planar chiral cationic iridium complex [Cp*Ir(η5-2-methyl-oxodienyl)][OT f] () following the counterion strategy, where anion metathesis by Δ-TRISPHAT generates the two diastereomers (pR, pS)-[Cp*Ir(η5-2-methyl-oxodienyl)][Δ-TRISPHAT] (, ). Upon fractional crystallization both compounds were separated as confirmed by 1H nuclear magnetic resonance (NMR) and circular dichroism studies recorded in solution. The latter represents the key-complex precursors for the enantioselective synthesis of metallated o-quinone methide complexes (, ). Chirality 25:449–454, 2013. © 2013 Wiley Periodicals, Inc.
    Mots-clés : ARC, chirality, circular dichroism, diastereomeric separation, NMR, POLE 1, quinone methides.


  • J. Moussa, K. M. - C. Wong, X. F. Le Goff, M. N. Rager, C. K. - M. Chan, V. W. - W. Yam, et H. Amouri, « Dinuclear Platinum(II) Terpyridyl Complexes with a para-Diselenobenzoquinone Organometallic Linker: Synthesis, Structures, and Room-Temperature Phosphorescence », Organometallics, vol. 32, nᵒ 17, p. 4985-4992.
    Résumé : We report the synthesis of a unique class of luminescent heterotrinuclear complexes of the general formulas [Pt(terpy){Cp*Ir-p-(?4-C6H4Se2)}Pt(terpy)][X]4 (X = OTf, 3a; PF6, 3b; BF4, 3c; ClO4, 3d; BPh4, 3e). In these coordination assemblies two Pt(terpy) moieties are held by a stable ?4-diseleno-p-benzoquinone complex [Cp*Ir-p-(?4-C6H4Se2)]. The molecular structures of solvates of 3a and 3b were ascertained by single-crystal X-ray diffraction study and confirmed the formation of the target molecules. The solid-state packing of two of these complexes confirms the presence of π?π and Pt···Pt interactions among individual units providing a 1D supramolecular chain for 3a, while a dimer species is obtained for 3b, illustrating the effect of the counterion on directing the crystal packing of the individual molecules. All compounds show phosphorescence in the red region (685?705 nm) in fluid solution and in the solid state at room temperature, unlike the analogous compound Pt(terpy){Cp*Ir-p-(?4-C6H4S2)}Pt(terpy)][CF3SO3]4 obtained with a dithiobenzoquinone organometallic linker, which is only luminescent at low temperature.
    Mots-clés : ARC, POLE 1.

2012



  • H. Amouri, C. Desmarets, et J. Moussa, « Confined Nanospaces in Metallo-Cages: Guest Molecules, Weakly Encapsulated Anions, and Catalyst Sequestration », Chemical Reviews, vol. 112, nᵒ 4, p. 2015-2041.


  • A. Damas, B. Ventura, J. Moussa, A. D. Esposti, L. - M. Chamoreau, A. Barbieri, et H. Amouri, « Turning on Red and Near-Infrared Phosphorescence in Octahedral Complexes with Metalated Quinones », Inorganic Chemistry, vol. 51, nᵒ 3, p. 1739-1750.
    Résumé : We report the synthesis of π-bonded ruthenium, rhodium, and iridium o-benzoquinones [Cp*M(o-C6H4O2)]n [M = Ru (2), n = 1?; Rh (3), n = 0; Ir (4), n = 0] following a novel synthetic procedure. Compounds 2?4 were fully characterized by spectroscopic methods and used as chelating organometallic linkers, ?OM-linkers?, toward luminophore bricks such as Ru(bpy)22+, Rh(ppy)2+, and Ir(ppy)2+ (bpy = 2,2?-bipyridine; ppy = 2-phenylpyridine) for the design of a novel family of octahedral bimetallic complexes of the general formula [(L-L)2M(OM-linkers)][X]m (X = counteranion; m = 0, 1, 2) whose luminescent properties depend on the choice of the OM-linker and the luminophore brick. Thus, dinuclear assemblies such as [(bpy)2Ru(2)][OTf] (5-OTf), [(bpy)2Ru(2)][?-TRISPHAT] (5-?T) {TRISPHAT = tris[tetrachlorobenzene-1,2-bis(olato)]phosphate}, [(bpy)2Ru(3)][OTf]2 (6-OTf), [(bpy)2Ru(4)][OTf]2 (7-OTf), [(bpy)2Ru(4)][?-TRISPHAT]2 (7-?T), [(ppy)2Rh(2)] (8), [(ppy)2Rh(3)][OTf] (9-OTf), [(ppy)2Rh(4)][OTf] (10-OTf), [(ppy)2Rh(4)][?-TRISPHAT] (10-?T), [(ppy)2Ir(2)] (11), [(ppy)2Ir(3)][OTf] (12-OTf), [(ppy)2Ir(4)][OTf] (13-OTf), and [(ppy)2Ir(4)][?-TRISPHAT] (13-?T) were prepared and fully characterized. The X-ray molecular structures of three of them, i.e., 5-OTf, 8, and 11, were determined. The structures displayed a main feature: for instance, the two oxygen centers of the OM-linker [Cp*Ru(o-C6H4O2)]? (2) chelate the octahedral chromophore metal center, whether it be ruthenium, rhodium, or iridium. Further, the carbocycle of the OM-linker 2 adopts a ?4-quinone form but with some catecholate contribution due to metal

    coordination. All of these binuclear assemblies showed a wide absorption window that tailed into the near-IR (NIR) region, in particular in the case of the binuclear ruthenium complex 5-OTf with the anionic OM-linker 2. The latter feature is no doubt related to the effect of the OM-linker, which lights up the luminescence in these homo- and heterobinuclear compounds, while no effect has been observed on the UV?visible and emission properties because of the counteranion, whether it be triflate (OTf) or ?-TRISPHAT. At low temperature, all of these compounds become luminescent; remarkably, the o-quinonoid linkers [Cp*M(o-C6H4O2)]n (2?4) turn on red and NIR phosphorescence in the binuclear octahedral species 5?7. This trend was even more observable when the ruthenium OM-linker 2 was employed. These assemblies hold promise as NIR luminescent materials, in contrast to those made from organic 1,2-dioxolene ligands that conversely are not emissive.
    Mots-clés : ARC, POLE 1.


  • J. Dubarle-Offner, M. R. Axet, L. M. Chamoreau, H. Amouri, et A. L. Cooksy, « Enantiomerically Pure, Planar Chiral Cp*Ru Complexes: Synthesis, Molecular Structures, DFT and Coordination Properties », Organometallics, vol. 31, nᵒ 12, p. 4429-4434.
    Résumé : Reaction of (S)-1-(2-chlorophenyl)ethanol with [Cp*Ru(CH3CN)3][OTf] provides the single diastereomer (Sp)-[Cp*Ru(?6-(S)-1-(2-chlorophenyl)ethanol)][OTf] ((Sp,S)-1), in which the metal center is preferentially placed on one side of the arene ring. The other enantiomer (R)-1-(2-chlorophenyl)ethanol provides the planar chiral ruthenium compound (Rp,R)-1. The structures of both enantiomers were ascertained by single-crystal X-ray diffraction. These compounds can be used as precursors to prepare the enantiopure metalated phosphino ligands (Sp)-[Cp*Ru(?6-(S)-1-(2-diphenylphosphinophenyl)ethanol)][OTf] ((Sp,S)-2) and (Rp)-[Cp*Ru(?6-(R)-1-(2-diphenylphosphinophenyl)ethanol)][OTf] ((Rp,R)-2), in which the ?PPh2 unit is attached to a chiral metalated π-arene platform. The chiral planar phosphine ligands react with [AuCl(tht)] to give heterobinuclear gold complexes with planar chirality, [AuCl((Sp,S)-2)] ((Sp,S)-3) and [AuCl((Rp,R)-2)] ((Rp,R)-3), as confirmed by their CD traces. Our method provides an entry to the preparation of a wide range of optically pure coordination compounds with potentially important properties.
    Mots-clés : ARC, POLE 1.


  • B. Matt, J. Moussa, L. - M. Chamoreau, C. Afonso, A. Proust, H. Amouri, et G. Izzet, « Elegant Approach to the Synthesis of a Unique Heteroleptic Cyclometalated Iridium(III)-Polyoxometalate Conjugate », Organometallics, vol. 31, nᵒ 1, p. 35-38.
    Résumé : A novel heteroleptic cyclometalated iridium(III) complex with one picolinic acid derivative bearing a pendant terminal alkynyl tether has been prepared following a new synthetic route. This pendant alkynyl tether can be further engaged in palladium C?C coupling reactions, allowing its grafting to a Keggin-type polyoxometalate and thus providing a unique iridio-POM conjugate.
    Mots-clés : ARC, E-POM, POLE 1, POLE 2, POM.


  • J. Moussa, A. Damas, L. - M. Chamoreau, M. N. Rager, et H. Amouri, « Unique Type of BF2-Capped Tetraoxobenzene π-Complexes of “Cp*M”: Novel Organometallic Backbones for the Self-Assembly of Porous Networks », European Journal of Inorganic Chemistry, vol. 2012, nᵒ 9, p. 1342–1346.
    Résumé : The synthesis of two novel organometallic π complexes of a BF2-capped tetraoxobenzene (TOB) of the general formulae [Cp*M-η6-BF2-TOB-BF2] (M = Ir, 2a; M = Rh, 2b) is reported together with their molecular structures ascertained by single-crystal X-ray diffraction studies. Complexes 2a and 2b are isostructural and show the formation of 3D porous supramolecular networks. Interestingly the supramolecular networks arise from the zwitterionic nature of 2a and 2b. Indeed, the individual molecules self-assemble through the teamwork of dipolar H···F hydrogen and C···F halogen bonds, which leads to the formation of 3D networks with empty channels. These complexes hold promise for the design of a new class of porous materials with useful properties.
    Mots-clés : ARC, Iridium, POLE 1, Porous materials, Rhodium, Self-assembly, Supramolecular chemistry.

2011


  • H. Amouri, « Metal-Stabilized o-Quinone Methides, Thioquinones, and Selenoquinones: Trapping Important Reactive Intermediates and Beyond », Synlett, nᵒ 10, p. 1357-1369.
    Résumé : Quinone methides (quinomethanes) act as important intermediates in organic syntheses, as well as in chemical and biological processes. However, examples of such isolated species are scarce owing to their high reactivity. Other important reactive intermediates are thio- and selenoquinones. However, unlike quinones, they are highly unstable and consequently do not exist in nature, hence their chemical and biological properties remain unknown. In this account, we describe the first isolation of the above important reactive intermediates, by pi-coordination to a (pentamethylcyclopentadienyl) iridium (Cp*Ir) moiety, and their X-ray molecular structures. Further, the reactivity of such trapped intermediates is reported. For instance, the metalated o-quinone methide underwent an unusual cycloaddition reaction compared with the free o-quinone methide, while the metalated thioquinones were successfully used as organometallic linkers (OM-linkers) to construct luminescent coordination assemblies. The anticancer activity of the selenoquinone metalated complex was studied, together with related oxygen and sulfur analogues, and remarkably it was shown to be the only cytotoxic compound with a comparable activity to cisplatin.
    Mots-clés : anticancer activity, ARC, bioreductive alkylating-agents, cp-asterisk-ir, crystal-structure, diels-alder reaction, hydroxybenzyl alcohols, Iridium, luminescence properties, metal-stabilized o-quinone methides, metal-stabilized selenoquinones, metal-stabilized thioquinones, molecular-structure, photochemical-transformations, POLE 1, Reactive intermediates, regioselective ortho-functionalization, spectroscopic evidence.


  • M. Barbazanges, M. Augé, J. Moussa, H. Amouri, C. Aubert, C. Desmarets, L. Fensterbank, V. Gandon, M. Malacria, et C. Ollivier, « Enantioselective IrI-Catalyzed Carbocyclization of 1,6-Enynes by the Chiral Counterion Strategy », Chemistry – A European Journal, vol. 17, nᵒ 49, p. 13789–13794.
    Résumé : Enantioenriched bicyclo[4.1.0]hept-2-enes were synthesized by IrI-catalyzed carbocyclization of 1,6-enynes. No chiral ligands were used, CO and PPh3 were the only ligands bound to iridium. Instead, the stereochemical information was localized on the counterion of the catalyst, generated in situ by reaction of Vaska’s complex (trans-[IrCl(CO)(PPh3)2]) with a chiral silver phosphate. Enantiomeric excesses up to 93 % were obtained when this catalytic mixture was used. 31P NMR and IR spectroscopy suggest that formation of the trans- [Ir(CO)(PPh3)2]+ moiety occurs by chlorine abstraction. Moreover, density functional theory calculations support a 6-endo-dig cyclization promoted by this cationic moiety. The chiral phosphate anion (OP*) controls the enantioselectivity through formation of a loose ion pair with the metal center and establishes a CH⋅⋅⋅OP* hydrogen bond with the substrate. This is a rare example of asymmetric counterion-directed transition-metal catalysis and represents the first application of such a strategy to a CC bond-forming reaction.
    Mots-clés : ARC, chirality, COS, enynes, homogeneous catalysis, ion pairs, Iridium, MACO, POLE 1.


  • E. Benedetti, A. Simonneau, A. Hours, H. Amouri, A. Penoni, G. Palmisano, M. Malacria, J. - P. Goddard, et L. Fensterbank, « (Pentamethylcyclopentadienyl)Iridium Dichloride Dimer [IrCp*Cl2]2: A Novel Efficient Catalyst for the Cycloisomerizations of Homopropargylic Diols and N-Tethered Enynes », Advanced Synthesis & Catalysis, vol. 353, nᵒ 11-12, p. 1908–1912.
    Résumé : (Pentamethylcyclopentadienyl)iridium dichloride dimer [IrCp*Cl2]2-catalyzed hydroalkoxylation of bis-homopropargylic alcohols provides an efficient access to dioxabicyclo[2.2.1]ketals. The cycloisomerizations proceed under mild conditions, with low catalytic loadings and short reaction times. This new protocol involving an Ir(III) catalyst also promoted the cycloisomerization of nitrogen-tethered 1,6-enynes to give azabicyclo[4.1.0]heptenes, enhancing the synthetic potential of our method.
    Mots-clés : ARC, bicyclic compounds, COS, Cycloisomerization, enynes, homogeneous catalysis, iridium(III), MACO, POLE 1.


  • C. Desmarets, I. Azcarate, G. Gontard, et H. Amouri, « A Rigid Angular Bidentate Ligand for the Design of a New Class of Coordination Polymers Based on Silver(I) Salts – Influence of the Anion on Coordination Assemblies », European Journal of Inorganic Chemistry, vol. 2011, nᵒ 29, p. 4558–4563.
    Résumé : The synthesis of a new family of coordination polymers [AgL2X]n (1a, X = CF3SO3; 1b, X = BF4; 1c, X = NO3; 1d, X = PF6) using 5-methoxy-1,3-bis(pyridin-3-ylethynyl)benzene (L2) as the self-assembling ligand is described. All compounds have been fully characterized by spectroscopic techniques and elemental analysis. In particular the X-ray molecular structures of 1a and 1b are reported and confirm the formation of 1D silver(I) chains. Their arrangements are described as a function and the nature of the anion. The supramolecular product 1a exhibits argentophilic Ag···Ag interactions to afford infinite double chains. Additionally, η1–AgI–π interactions lead to the formation of a network of stacked layers of double chains. In contrast, 1b lacks metal–counterion bonding and is constituted of infinite coordination polymers, which are held together by π–π interactions. The pivotal role of the counteranions on the overall packing arrangement of the polymers is presented and discussed.
    Mots-clés : ARC, Coordination chemistry, Coordination polymers, Ligand design, POLE 1, Self-assembly, silver.

2010



  • H. Amouri, J. Moussa, A. K. Renfrew, P. J. Dyson, M. N. Rager, et L. - M. Chamoreau, « Discovery, Structure, and Anticancer Activity of an Iridium Complex of Diselenobenzoquinone », Angewandte Chemie International Edition, vol. 49, nᵒ 41, p. 7530–7533.
    Mots-clés : ARC, coordination modes, Iridium, POLE 1, quinones, Reactive intermediates, selenium.


  • M. R. Axet, M. Barbazanges, M. Augé, C. Desmarets, J. Moussa, C. Ollivier, C. Aubert, L. Fensterbank, V. Gandon, M. Malacria, L. M. Chamoreau, et H. Amouri, « Metalated-Arene-Phosphino Ligands: A Novel Approach to Open-Sided Gold Compounds », Organometallics, vol. 29, nᵒ 24, p. 6636-6638.
    Résumé : A novel type of metalated phosphino ligands, [Cp*Ru(?6-arene-PPh2)][OTf] (2a?d-OTf), has been prepared in which the ?PPh2 unit is attached to a metalated π-arene platform. This unique class of ligands 2a?d are converted to open-sided cationic gold complexes 3a?d upon treatment with [AuCl(tht)]. The structure of one of these compounds, [Cp*Ru(?6-C6H5?PPh2?Au-Cl)][OTf] (3a-OTf), was ascertained by single-crystal X-ray diffraction. Preliminary studies suggest that cationic complex 3a is active in metal-catalyzed cycloisomerization reactions.
    Mots-clés : ARC, COS, MACO, POLE 1.


  • A. Damas, J. Moussa, M. N. Rager, et H. Amouri, « Chiral octahedral bimetallic assemblies with Δ-TRISPHAT as counter anion: Design, anion metathesis, and Cp*Ir as a probe for chiral recognition », Chirality, vol. 22, nᵒ 10, p. 889–895.
    Résumé : The chiral octahedral bimetallic assemblies [(bpy)2Ru(o-LIr)][CF3SO3]2 (2), [(ppy)2Rh(o-LIr)][NO3] (7) and [(ppy)2Ir(o-LIr)][NO3] (8) featuring chelating organometallic linker [Cp*Ir(η4-o-benzoquinone)] (o-LIr) have been prepared and fully characterized. Anion metathesis following a convenient procedure allowed the preparation of the related diastereomers [Δ-(bpy)2Ru(o-LIr)][Δ-TRISPHAT]2 (2a) and [Λ-(bpy)2Ru(o-LIr)][Δ-TRISPHAT]2 (2b) as well as the octahedral rhodium [(Δ, Λ)-(ppy)2Rh(o-LIr)][Δ-TRISPHAT] (7a, 7b) and iridium [(Δ, Λ)-(ppy)2Ir(o-LIr)][Δ-TRISPHAT] (8a, 8b) bimetallic assemblies. 1H NMR studies in solution carried out on these compounds showed different behavior. For instance, the rhodium and iridium compounds exhibited weak chiral recognition in contrast the ruthenium compounds allowed facile differentiation between the two diastereomers suggesting that chiral recognition occurs between the enantiopure anion and the cationic part of the molecule. Chirality, 2010. © 2010 Wiley-Liss, Inc.
    Mots-clés : ARC, chirality, enantiomeric differentiation, ion pairs, NMR, organometallic linker, POLE 1, π–π interaction.


  • A. Damas, B. Ventura, M. R. Axet, A. D. Esposti, L. - M. Chamoreau, A. Barbieri, et H. Amouri, « Organometallic Quinonoid Linkers: A Versatile Tether for the Design of Panchromatic Ruthenium(II) Heteroleptic Complexes », Inorganic Chemistry, vol. 49, nᵒ 23, p. 10762-10764.
    Résumé : The synthesis, X-ray structure determination, and photophysical investigation of a novel series of heteroleptic ruthenium(II) polypyridine complexes with organometallic linkers are reported. The displayed panchromatic absorption features are assigned by means of time-dependent density functional theory studies.
    Mots-clés : ARC, POLE 1.


  • D. B. Grotjahn, J. E. Kraus, H. Amouri, M. - N. Rager, A. L. Cooksy, A. J. Arita, S. A. Cortes-Llamas, A. A. Mallari, A. G. DiPasquale, C. E. Moore, L. M. Liable-Sands, J. D. Golen, L. N. Zakharov, et A. L. Rheingold, « Multimodal Study of Secondary Interactions in Cp*Ir Complexes of Imidazolylphosphines Bearing an NH Group », Journal of the American Chemical Society, vol. 132, nᵒ 23, p. 7919-7934.
    Résumé : Hydrogen bonding phenomena are explored using a combination of X-ray diffraction, NMR and IR spectroscopy, and DFT calculations. Three imidazolylphosphines R2PImH (ImH = imidazol-2-yl, R = t-butyl, i-propyl, phenyl, 1a?1c) and control phosphine (i-Pr)2PhP (1d) lacking an imidazole were used to make a series of complexes of the form Cp*Ir(L1)(L2)(phosphine). In addition, in order to suppress intermolecular interactions with either imidazole nitrogen, 1e, a di(isopropyl)imidazolyl analogue of 1b was made along with its doubly 15N-labeled isotopomer to explore bonding interactions at each imidazole nitrogen. A modest enhancement of transfer hydrogenation rate was seen when an imidazolylphosphine ligand 1b was used. Dichloro complexes (L1 = L2 = Cl, 2a?2c,2e) showed intramolecular hydrogen bonding as revealed by four X-ray structures and various NMR and IR data. Significantly, hydride chloride complexes [L1 = H, L2 = Cl, 3a?3c and 3e-(15N)2] showed stronger hydrogen bonding to chloride than hydride, though the solid-state structure of 3b evinced intramolecular Ir?H···H?N bonding reinforced by intermolecular N···H?N bonding between unhindered imidazoles. These results are compared to literature examples, which show variations in preferred hydrogen bonding to hydride, halide, CO, and NO ligands. Surprising differences were seen between the dichloro complex 2b with isopropyl groups on phosphorus, which appeared to exist as a mixture of two conformers, and related complex 2a with tert-butyl groups on phosphorus, which exists in chlorinated solvents as a mixture of conformer 2a-endo and chelate 5a-Cl, the product of ionization of one chloride ligand. This difference became apparent only through a series of experiments, especially 15N chemical shift data from 2D 1H?15N correlation. The results highlight the difficulty of characterizing hemilabile, bifunctional complexes and the importance of innocent ligand substituents in determining structure and dynamics.
    Mots-clés : ARC, POLE 1.

2009

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    A. Aissa, M. Debbabi, M. Gruselle, R. Thouvenot, A. Flambard, P. Gredin, P. Beaunier, et K. Tonsuaadu, « Sorption of tartrate ions to lanthanum (III)-modified calcium fluor- and hydroxyapatite », Journal of Colloid and Interface Science, vol. 330, nᵒ 1, p. 20-28.
    Résumé : The present article details the formation of lanthanum-modified apatites and the binding process of tartrate ions with these obtained apatites. Chemical analyses, FT-IR and (31)P NMR spectroscopies XRD, powder, TGA, and TEM analyses were employed for studying the reaction between Ca(10)(PO(4))(6)(OH)(2)(HAp) or Ca(10)(PO(4))(6)(F)(2) (FAp) and LaCl(3). The reaction was found to take place mainly through partial dissolution of the apatite followed by precipitation of a new phase containing lanthanum phosphate. When La(3+) was introduced in the presence of L(+)-tartaric acid (TAH(2)), no fundamental changes were observed in the HAp or FAp structures. However, there did occur a formation of a new phase of Ca or/and La tartrate salt. (C) 2008 Elsevier Inc. All rights reserved.
    Mots-clés : apatite, ARC, catalysts, E-POM, ERMMES, Fluorapatite, Hydroxyapatite, Lanthanum, mas nmr, metal-ions, MMMAX, molecular-oxygen, oxidation, POLE 1, POLE 2, POM, rare-earth-elements, ru-hydroxyapatite, surface sites, Tartaric acid.

  • H. Amouri, J. Moussa, M. Malacria, et V. Gandon, « Cyclopentadienyl Ligands as Perfect Anion Receptors: Teamwork between pi-Anion Interaction and C-H center dot center dot center dot Anion Hydrogen Bonds », Crystal Growth & Design, vol. 9, nᵒ 12, p. 5304-5310.
    Résumé : Electron-deficient arenes are now recognized as potent anion receptors, mainly through the establishment of pi-anion interactions. Cyclopentadienyl ligands (Cp's) also belong to the family of arenes that exhibit very low electron density at their centroid due to the presence of the metal oil one side. As such, they also work as anion receptors. A closer look at the reported X-ray structures in which all anion is in short contact with the Cp framework reveals that in most cases the five-membered ring is substituted, generally pentamethylated (Cp*). This is quite surprising since Cp* is electron-richer than the unsubstituted Cp ligand. This computational Study shows that Cp* functions as a ring bearing a gemstone: the anion establishes a strong pi-interaction with the centroid, but this is not sufficient to hold it straight. For that matter, each methyl group develops a C-H center dot center dot center dot anion hydrogen bond, thus working as a claw to prevent the gem from falling. Although individually small, the interaction energy provided by the five methyl groups makes the M-Cp* a perfect anion receptacle.
    Mots-clés : ARC, atomic charges, COS, crystal-structures, electron-deficient, gaussian-type basis, iridium complexes, MACO, molecular-orbital methods, organic-molecules, pentamethylcyclopentadienyliridium complexes, POLE 1, ring-methyl activation, x-ray structure.


  • C. Desmarets, F. Poli, X. F. L. Goff, K. Müller, et H. Amouri, « A unique type of a dicobalt cage templated by a weakly coordinated hexafluorophosphate anion: design, structure and solid-state NMR investigations », Dalton Transactions, nᵒ 47, p. 10429-10432.
    Résumé : A dinuclear cobalt capsule [PF6⊂(CH3CN)2(Co2L4)][PF6]3 (2), (L = bis-benzimidazole-1,3-phenylene) has been prepared using a self-assembly approach. This unique class of cage is perfectly designed to encapsulate weakly coordinated anions, i.e. BF4− and PF6−via an M [] anion weak interaction as illustrated by X-r...
    Mots-clés : ARC, POLE 1.


  • C. Desmarets, C. Policar, L. - M. Chamoreau, et H. Amouri, « Design, Self-Assembly, and Molecular Structures of 3D Copper(II) Capsules Templated by BF4– Guest Anions », European Journal of Inorganic Chemistry, vol. 2009, nᵒ 29-30, p. 4396–4400.
    Résumé : The synthesis of two 3D M2L4 copper(II) capsules, [BF4⊂(CH3CN)2Cu2(L1)4][BF4]3 (1) and [BF4⊂(BF4)2Cu2(L1)4][BF4] (2), by using 1,3-(benzimidazol-1-ylmethyl)-2,5-dimethoxy-4,6-dimethylbenzene (L1) as a semirigid exobidentate ligand and [Cu(CH3CN)4][BF4]2 as a metallobrick is reported. Single-crystal X-ray diffraction studies show the encapsulation of a BF4– anion in 1 and 2. Moreover, 2 displayed three coordinated BF4– anions, which is rare in supramolecular coordination host–guest chemistry. Remarkably, in both metallocages the weakly coordinated BF4– anion acts as a template and interacts with the metal center through a weak Cu···F contact. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)
    Mots-clés : ARC, Cage compounds, Copper, Encapsulation, Host–guest systems, POLE 1, Self-assembly.


  • J. Moussa, V. Gandon, M. N. Rager, M. Malacria, L. - M. Chamoreau, et H. Amouri, « An Unusual Anion–π Interaction in an ;rido Organometallic Assembly: Synthesis, First Crystal Structure, and Computational Study », European Journal of Inorganic Chemistry, vol. 2009, nᵒ 25, p. 3703–3707.
    Résumé : The organometallic assembly [Cp*Ir(η6-C6H2O4)(BF2)2(CF3SO3)][Cp*Ir(μ-Cl)3IrCp*] (3) was prepared from [Cp*Ir(solvent)3][OTf]2 (2) and 1,2,4,5 tetrahydroxybenzene (THB, 1) in acetone, in the presence of an excess amount of BF3·2H2O. Assembly 3 was fully characterized by multinuclear NMR spectroscopy. Remarkably, the X-ray molecular structure of 3 shows that an anion–π interaction occurs between the neutral component Cp*Ir(η6-C6H2O4)(BF2)2 of the assembly and the CF3SO3 anion of the cationic species [Cp*Ir(μ-Cl)3IrCp*]. Computational analysis was carried out on 3 to unravel the nature of this noncovalent interaction. Such an example could serve as a model to explain the important role of anions in organometallic chemistry and asymmetric catalysis. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)
    Mots-clés : ARC, Arene ligands, Boron, COS, density functional calculations, Iridium, MACO, Pi interactions, POLE1, Reactive intermediates.


  • J. Moussa, M. N. Rager, L. M. Chamoreau, L. Ricard, et H. Amouri, « Unprecedented π-Bonded Rhodio- and Iridio-o-Benzoquinones as Organometallic Linkers for the Design of Chiral Octahedral Bimetallic Assemblies », Organometallics, vol. 28, nᵒ 2, p. 397-404.
    Résumé : We report the first synthesis of π-bonded rhodio- and iridio-o-benzoquinones [Cp*M(o-benzoquinone)] (M = Rh (3a); M = Ir (3b)) following a novel synthetic procedure and their use as chelating organometallic linkers for the design of a new family of chiral octahedral bimetallic complexes, 4?9. The X-ray molecular structure of [(bpy)2Ru(3b)][OTf]2 (5) is presented. These assemblies hold promise for new properties relative to those made from organic bidentate ligands.
    Mots-clés : ARC, POLE1.


  • C. Train, T. Nuida, R. Gheorghe, M. Gruselle, et S. -ichi Ohkoshi, « Large Magnetization-Induced Second Harmonic Generation in an Enantiopure Chiral Magnet », Journal of the American Chemical Society, vol. 131, nᵒ 46, p. 16838-16843.
    Résumé : The absence of centrosymmetry in the enantiopure chiral magnet [N(CH3)(n-C3H7)2(C*H(CH3)C2H5)][MnIICrIII(ox)3] allows the observation of bulk second harmonic generation (SHG) in this material. At low temperature, the onset of magnetization gives birth to a magnetization-induced SHG (MSHG) contribution. With an angular shift of 13.1° upon magnetization reversal, the MSHG effects appear to be much larger than the corresponding linear magneto-optical effects. Thanks to the single-crystalline state of the sample, the variation of the signal with the orientation of the magnetic field and/or the angle between the polarization of the incident radiation and the outgoing SHG signal in the paramagnetic and ferromagnetic phases is reproduced and well-understood through the use of a symmetry-based analysis of the nonlinear susceptibility tensor.
    Mots-clés : ARC, ERMMES, MMMAX, POLE 1, POLE 2.
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