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Publications

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2017



  • J. Moussa, A. Loch, L. - M. Chamoreau, A. Degli Esposti, E. Bandini, A. Barbieri, et H. Amouri, « Luminescent Cyclometalated Platinum Complexes with π-Bonded Catecholate Organometallic Ligands », Inorganic Chemistry, vol. 56, nᵒ 4, p. 2050-2059.
    Résumé : A series of cyclometalated platinum(II) complexes of the type [(ppy)Pt(LM)]n+ (n = 0, 1) with π-bonded catecholates acting as organometallic ligands (LM) have been prepared and characterized by analytical techniques. In addition, the structures of two complexes of the series were determined by single-crystal X-ray diffraction. The packing shows the formation of a 1D supramolecular assembly generated by dPt–πCp* interactions among individual units. All complexes are luminescent in the solid state and in solution media. The results of photophysics have been rationalized by means of density functional theory (DFT) and time-dependent DFT investigations.
    Mots-clés : ARC, POLE 1.


  • S. B. Moussa, H. Bachouâ, M. Gruselle, P. Beaunier, A. Flambard, et B. Badraoui, « Hybrid organic-inorganic materials based on hydroxyapatite structure », Journal of Solid State Chemistry, vol. 248, p. 171-177.
    Résumé : The present article details the formation of calcium hydroxyapatite synthesized by the hydrothermal way, in presence of glycine or sarcosine. The presence of these amino-acids during the synthetic processes reduces the crystalline growthing through the formation of hybrid organic-inorganic species The crystallite sizes are decreasing and the morphology is modified with the increase of the amino-acid concentration.
    Mots-clés : ARC, ERMMES, Glycine, Hydrothermal synthesis, Hydroxyapatite, POLE 1, POLE 2, Sarcosine.

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 structural 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

  • H. Amouri, « Selenoquinone-derived active organometallic complexes, methods for synthezing same and uses thereof », U.S. Patent US 8 367 723 B2 extension JP 5 746 693 et EP 2 456 776 B1.


  • 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.
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