Jean-Yves Saillard

Université de Rennes 1, Roazhon, Brittany, France

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Publications (160)657.76 Total impact

  • [Show abstract] [Hide abstract]
    ABSTRACT: An air- and moisture-stable nanoscale polyhydrido copper cluster [Cu32 (H)20 {S2 P(OiPr)2 }12 ] (1H ) was synthesized and structurally characterized. The molecular structure of 1H exhibits a hexacapped pseudo-rhombohedral core of 14 Cu atoms sandwiched between two nestlike triangular cupola fragments of (2×9) Cu atoms in an elongated triangular gyrobicupola polyhedron. The discrete Cu32 cluster is stabilized by 12 dithiophosphate ligands and a record number of 20 hydride ligands, which were found by high-resolution neutron diffraction to exhibit tri-, tetra-, and pentacoordinated hydrides in capping and interstitial modes. This result was further supported by a density functional theory investigation on the simplified model [Cu32 (H)20 (S2 PH2 )12 ]. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    Chemistry - A European Journal 04/2015; DOI:10.1002/chem.201501122 · 5.70 Impact Factor
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    ABSTRACT: An original copper(I) iodide cluster of novel geometry obtained by using a diphosphine ligand is reported and is formulated [Cu6I6(PPh2(CH2)3PPh2)3] (1). Interestingly, this sort of "eared cubane" cluster based on the [Cu6I6] inorganic core can be viewed as a combination of the two known [Cu4I4] units, namely, the cubane and the open-chair isomeric geometries. The synthesis, structural and photophysical characterisations, as well as theoretical study of this copper iodide along with the derived cubane (3) and open-chair (2) [Cu4I4(PPh3)4] forms, were investigated. A new polymorph of the cubane [Cu4I4(PPh3)4] cluster is indeed presented (3). The structural differences of the clusters were analyzed by solid-state nuclear magnetic resonance spectroscopy. Luminescence properties of the three clusters were studied in detail as a function of the temperature showing reversible luminescence thermochromism for 1 with an intense orange emission at room temperature. This behavior presents different feature compared to the cubane cluster and completely contrasts with the open isomer, which is almost nonemissive at room temperature. Indeed, the thermochromism of 1 differs by a concomitant increase of the two emission bands by lowering the temperature, in contrast to an equilibrium phenomenon for 3. The luminescence properties of 2 are very different by exhibiting only one single band when cooled. To rationalize the different optical properties observed, density functional theory calculations were performed for the three clusters giving straightforward explanation for the different luminescence thermochromism observed, which is attributed to different contributions of the ligands to the molecular orbitals. Comparison of 3 with its [Cu4I4(PPh3)4] cubane polymorphs highlights the sensibility of the emission properties to the cuprophilic interactions.
    Inorganic Chemistry 04/2015; DOI:10.1021/acs.inorgchem.5b00321 · 4.79 Impact Factor
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    ABSTRACT: A novel discrete [Ag21{S2P(OiPr)2}12](PF6) nanocluster has been synthesized and characterized by single-crystal X-ray diffraction and also NMR spectroscopy (1H, 31P), ESI mass spectrometry, and other analytic techniques (XPS, EDS, UV/Vis spectroscopy). The Ag21 skeleton has an unprecedented silver-centered icosahedron that is capped by eight additional metal atoms. The whole framework is protected by twelve dithiophosphate ligands. According to the spherical Jellium model, the stability of monocationic nanocluster can be described by an 8-electron superatom with 1S2 1P6 configuration, as confirmed by DFT calculations.
    Angewandte Chemie 01/2015; 127(12):n/a-n/a. DOI:10.1002/ange.201410332
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    ABSTRACT: Ligand exchange reactions between [Cp*Ru(NCMe)3][PF6], where Cp* represents η(5)-C5Me5, and the polycyclic aromatic hydrocarbons (PAHs) pyrene, acenaphthylene and fluoranthene afforded the known [Cp*Ru(η(6)-pyrene)][PF6] () and the new mixed sandwiches [Cp*Ru(η(6)-acenaphthylene)][PF6] () and [Cp*Ru(η(6)-fluoranthene)][PF6] (), respectively, isolated in quantitative yields (94-100%). Complex is formed as a mixture of two isomers: as the major product where the [Cp*Ru(+)] moiety is coordinated to the naphthalene fragment of fluoranthene, and with the coordination of the arenophile to the peripheral benzene ring, in a 90/10 spectroscopic ratio. The composition and identity of the complexes were deduced by elemental analysis, (1)H and (13)C multidimensional NMR spectroscopy, and mass spectrometry. Compounds , and have been characterized using X-ray structural investigations. That showed that the [Cp*Ru(+)] unit is η(6)-attached to one of the two naphthalene rings in each complex. Heating and at 90 °C in CD3NO2 solutions or heating at 120 °C in the solid phase did not provide any evidence for thermally induced intramolecular inter-ring haptotropic rearrangements. These rearrangements were modelled by DFT calculations which indicated rather high activation energies.
    Dalton Transactions 11/2014; 44(1). DOI:10.1039/c4dt02736a · 4.10 Impact Factor
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    ABSTRACT: Two luminescent dinuclear gold(i) species, namely diselenophosphinate [Au2[small mu ]-Se2P((CH2)2Ph)22] and dithiophosphinate [Au2[small mu ]-S2P((CH2)2Ph)22], exhibiting interesting structural, absorption and emission properties have been studied. In the solid state, both complexes exist in a dinuclear monomeric form, exhibiting no aurophilic interaction, and display similar photophysical properties. It is shown, using DFT computations, that Au-Au chemical bonding appears in the first excited state of these complexes, whereas such bonding does not exist in their ground state; Raman spectroscopy experiments, which bring to light the stretching of this new bond, confirm the theoretical results. Moreover, TDDFT computations permitted us to assign the observed absorption bands of the UV-visible spectra of the two species to LMCT transitions and to describe the emission.
    Physical Chemistry Chemical Physics 10/2014; DOI:10.1039/C4CP03990D · 4.20 Impact Factor
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    ABSTRACT: The structure of a nanospheric polyhydrido copper cluster, [Cu20(H)11{S2P(O(i)Pr)2}9], was determined by single-crystal neutron diffraction. The Cu20 cluster consists of an elongated triangular orthobicupola constructed from 18 Cu atoms that encapsulate a [Cu2H5](3-) ion with an exceptionally short Cu-Cu distance. The 11 hydrides in the cluster display three different coordination modes to the Cu atoms: six μ3-hydrides in a pyramidal geometry, two μ4-hydrides in a tetrahedral cavity, and three μ4-hydrides in an unprecedented near square-planar geometry. The neutron data set was collected for 7 days on a small crystal with dimensions of 0.20 mm × 0.50 mm × 0.65 mm using the Spallation Neutron Source TOPAZ single-crystal time-of-flight Laue diffractometer at Oak Ridge National Laboratory. The final R-factor was 8.63% for 16,014 reflections.
    Inorganic Chemistry 10/2014; 53(20). DOI:10.1021/ic501747e · 4.79 Impact Factor
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    ABSTRACT: In this contribution, we report the synthesis of two series of compounds: 4-(arylvinyl)-1-methylpyrimidinium derivatives and tungsten pentacarbonyl complexes of 4-(arylvinyl)pyrimidines. Their second order non-linear properties, measured by Electric-Field Induced Second Harmonic generation (EFISH) method, and their photophysical behavior were thoroughly investigated and compared to the corresponding 4-arylvinyl)pyrimidines. A strong enhancement of the NLO response was observed upon methylation or complexation by W(CO)5 of the pyrimidine ring. DFT theoretical calculations were performed to provide complementary insights on the structure-properties relationships in particular concerning the amplitude of the NLO response.
    Dyes and Pigments 09/2014; 113. DOI:10.1016/j.dyepig.2014.09.028 · 3.47 Impact Factor
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    ABSTRACT: Ruthenaborane clusters have been modelled by performing density functional theory calculations using the B3LYP functional. The calculations gain insights into hydrogen storage and the H-H bond activation by ruthenaboranes. To study the nature of the chemical bond of H-2 molecules attached to ruthenaboranes, we carried out structural optimizations for different ruthenaborane clusters and determined transition state structures for their hydrogenation addition/elimination reactions. Calculations of the reaction pathways yielded different transition-state structures involving molecular hydrogen bonded to the cluster or formation of metal hydrides. The H-H bond of H-2 seems to be activated by the ruthenaborane clusters as activation energies of 24-42 kcal/mol were calculated for the H-2 addition reaction. The calculated Gibbs free energy for the H-2 addition reaction is 14-27 kcal/mol. The calculated activation energies and the molecular structures of the [(C5Me5) Ru2B10H16], [(C5Me5)Ru2B8H14] and [(C5Me5) Ru2B8H12] clusters with different degree of hydrogenation are compared. The mechanisms of the H-2 addition and elimination reactions of the studied clusters suggest that they might be useful as hydrogen storage materials due to their ability to activate the H-H bond. They also serve as an example of the ability of hypoelectronic metallaboranes to reversibly or irreversibly bind hydrogen.
    Journal of Organometallic Chemistry 07/2014; 761:1–9. DOI:10.1016/j.jorganchem.2014.03.001 · 2.30 Impact Factor
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    ABSTRACT: The first example of ligand protected Cu-Zn clusters is described. Reaction of [CpCu(CN(t)Bu)] with [Zn2Cp*2] yields [(CuCN(t)Bu)4(ZnCp*)4] () and [(CuCN(t)Bu)4(ZnCp*)3(ZnCp)] (). According to DFT calculations, the [Cu4Zn4] unit fulfils the unified superatom model for cluster valence shell closing.
    Chemical Communications 06/2014; 50(63). DOI:10.1039/c4cc03401e · 6.72 Impact Factor
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    ABSTRACT: Thirteen novel dipolar and V-shaped chromophores with pyranylidene electron-donating part, diazine electron-withdrawing part and various -linkers were synthesized. The extent of intramolecular charge transfer, structure-property relationships and optical properties were further investigated by UV/Vis absorption, electrochemistry and DFT calculations.
    Tetrahedron 02/2014; DOI:10.1016/j.tet.2014.02.071 · 2.82 Impact Factor
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    ABSTRACT: Three new halide-centered octanuclear silver(I) complexes, [Ag8(X){S2P(CH2CH2Ph)2}6](PF6), X = F(-), 1; Cl(-), 2; Br(-), 3; were prepared in the presence of the corresponding halide anions with silver(I) salts and dithiophosphinate ligands. Structure analyses displayed that a Ag8 cubic core can be modulated by the size effect of the central halide; however, an iodide-centered Ag8 cluster was not found under similar reaction conditions. Interestingly, a luminescent dodecanuclear silver(I) cluster, [Ag12(μ12-I)(μ3-I)4{S2P(CH2CH2Ph)2}6](I), 4; was then synthesized. The structure of 4 contains a novel μ12-I at the center of a cuboctahedral silver(I) atom cage, which is further stabilized by four additional μ3-I and six dithiophosphinate ligands. To the best of our knowledge, the μ12-I revealed in 4 is the highest coordination number for a halide ion authenticated by both experimental and computational studies. Previously, the μ12-I was only observed in [PyH][{TpMo(μ3-S)4Cu3}4(μ12-I)]. The synthetic details, spectroscopic studies including multinuclear NMR and ESI-MS, structure elucidations by single crystal X-ray diffraction, and photoluminescence of 4 are reported herein.
    Inorganic Chemistry 01/2014; 53(4). DOI:10.1021/ic402960e · 4.79 Impact Factor
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    ABSTRACT: Based on density functional calculations on model systems, the electronic structure of medium and large ligated palladium clusters is discussed herein. Among all the studied clusters, the electronic structure of \(\hbox {Pd}_{30}(\hbox {CO})_{26}(\hbox {PR}_3)_{10}\) , \(\hbox {Pd}_{69}(\hbox {CO})_{36}(\hbox {PR}_3)_{18}\) and \(\hbox {Pd}_{145}(\hbox {CO})_{56}(\hbox {PR}_3)_{30}\) clusters is analyzed in details. It is shown that the evolution of the band gap can be correlated to the average Pd-Pd bond length rather than n, the nuclearity of the cluster.
    Journal of Cluster Science 01/2014; 26(1):1-11. DOI:10.1007/s10876-014-0774-5 · 1.36 Impact Factor
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    Camille Latouche, C. W. Liu, Jean-Yves Saillard
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    ABSTRACT: Cu(I) and Ag(I) can form with 1,1-dithio(seleno) ligands various types of clusters, the framework of which being maintained by the metal–chalcogen bonds provided by the bridging ligands. The metal centers are generally tricoordinated and consequently possess an accepting orbital of valence s and/or p character. There is no formal metal–metal bonding, but only weak d10–d10 interactions which favor the overlap between the metal accepting orbitals. Their bonding combinations are generally suited for interacting with the occupied valence orbitals of an encapsulated anion. Thus, many of these clusters are able to encapsulate anions, a situation which tends to stabilize the whole structure through building of significant host–guest bonding. Not only is the anion encapsulation effect to stabilize the cluster cage, but it can also significantly modify its structure, or act as a template in the stabilization of species which would not exist as empty clusters. This paper reviews the synthesis, structure and bonding of all the known clusters of d10 metals decorated with 1,1-dichalchogeno ligands and containing entrapped atomic anions. Their structures are analyzed with respect to size and shape. The photoluminescence properties of some of them are discussed.
    Journal of Cluster Science 12/2013; DOI:10.1007/s10876-013-0671-3 · 1.36 Impact Factor
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    ABSTRACT: Whereas stable octanuclear clusters of the type M(I)8(E(∩)E)6 (M = Cu, Ag; E(∩)E = dithio or diseleno ligand) are known for being able to encapsulate a hydride or main-group anion under some circumstances, only the related hydride-containing heptanuclear [M(I)]7(H)(E(∩)E)6 and empty hexanuclear [M(I)]6(E(∩)E)6 species have been characterized so far. In this paper we investigate by the means of theoretical calculations and experiments the viability of empty and anion-centered clusters of the type [Cu(I)]7(X)(E(∩)E)6 and [Cu(I)]6(X)(E(∩)E)6 (X = vacancy, H or a main-group atom). The theoretical prediction for the existence of anion-containing heptanuclear species, the shape of which is modulated by the anion nature and size, have been fully confirmed by the synthesis and characterization of [Cu7(X){S2P(O(i)Pr)2}6] (X = H, Br). This consistency between experiment and theory allows us to predict the stability and shape-modulated structure of a whole series of [Cu(I)]7(X)(E(∩)E)6 (X = vacancy, H, O, S, halogen) and [Cu(I)]6(X)(E(∩)E)6 (X = H, halogen) clusters.
    Inorganic Chemistry 10/2013; 52(22). DOI:10.1021/ic402207u · 4.79 Impact Factor
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    ABSTRACT: M8L6 clusters (M = Cu(I), Ag(I); L = dichalcogeno ligand) are known for their ability to encapsulate various kinds of saturated atomic anions. Calculations on the models [M8(E2PH2)6](2+) (M = Cu(I), Ag(I); E = S, Se) and the ionic or neutral [M8(X)(E2PH2)6](q) (X = H, F, Cl, Br, O, S, Se, N, P, C) indicate that the cubic M8L6 cage adapts its shape for maximizing the host-guest bonding interaction. The interplay between size, covalent and ionic bonding favors either a cubic, tetracapped tetrahedral, or bicapped octahedral structure of the metal framework. Whereas the large third- and fourth-row main group anions maintain the cubic shape, a distortion toward a tetracapped tetrahedral arrangement of the metals occurs in the case of hydride, fluoride, and oxide. The distortion is strong in the case of hydride, weak in the case of fluoride, and intermediate in the case of oxide. Density functional theory (DFT) calculations predict a bicapped octahedral architecture in the case of nitride and carbide. These computational results are supported by X-ray structures, including those of new fluorine- and oxygen-containing compounds. It is suggested that other oxygen-containing as well as so far unknown nitride-containing clusters should be feasible. For the first time, the dynamical behavior of the encapsulated hydride has been investigated by metadynamics simulations. Our results clearly demonstrate that the interconversion mechanism between two identical tetracapped tetrahedral configurations occurs through a succession of M-H bonds breaking and forming which present very low activation energies and which involve a rather large number of intermediate structures. This mechanism is full in accordance with (109)Ag and (1)H state NMR measurements.
    Inorganic Chemistry 07/2013; 52(13):7752-7765. DOI:10.1021/ic400959a · 4.79 Impact Factor
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    ABSTRACT: Electro or chemical oxidation of ferrocenylmethylenepyran gave an ethanediferrocenylbispyrylium salt through the dimerization of a ferrocenylpyran radical-cation (C–C bond making). Electro or chemical reduction gave back the ferrocenylmethylenepyran (C–C bond breaking). This electrochemical reverse system constitutes an example of C–C bond making–breaking process in a metallocenyl series with rather high stability. DFT calculations and electrochemical studies were carried out in order to determine the electronic structure of the radical cation intermediate, the role of the ferrocenyl groups and the mechanism of the C–C bond making and C–C bond breaking processes. Reversible deprotonation of the ethanediferrocenylbispyrylium salt afforded an extended diferrocenylbismethylenepyran, which was subsequently reversibly oxidized to an ethenediferrocenylbispyrylium salt. X-Ray crystallographic data of diferrocenylbismethylenepyran and ethenediferrocenylbispyrylium salt allowed to determine the molecular movements, which come with the electron transfer (ET). A comparison with the behavior of the corresponding isoelectronic bisdithiafulvenes (extended TTF) and bisdithiolium salts was made.
    New Journal of Chemistry 06/2013; 37(7):2066-2081. DOI:10.1039/C3NJ41126E · 3.16 Impact Factor
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    ABSTRACT: Primary and secondary amines react with ethynylcobalticinium under mild conditions in the absence of a catalyst and an additional solvent to give quantitative yields of dark-red microcrystalline cobalticinium trans-enamines that show a remarkable push-pull electronic structure.
    Chemical Communications 05/2013; 49(52). DOI:10.1039/c3cc42211a · 6.72 Impact Factor
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    ABSTRACT: Full geometry optimization has been carried out for all the low-energy isomers of M(indenyl)2 (M = Sc–Ni, Y–Mo, Re, Ru–Pd). Depending on the electron-richness of the molecule, indenyl adopts various hapticities, some of them involving full or partial coordination of the C6 ring. Our results suggest that a judicious choice of substituents on the ligands should lead to the stabilization of η6-coordinated indenyl ligands. Indenyl is also shown to be quite flexible with respect to the spin ground state. Substituted iron and nickel bis-indenyl species should be characterizable in their triplet state. Thus, both from the point of view of coordination and the metal spin ground state, indenyl and cyclopentadienyl appear to behave quite differently.
    New Journal of Chemistry 05/2013; 37(8):-. DOI:10.1039/C3NJ00196B · 3.16 Impact Factor
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    ABSTRACT: An unprecedented air-stable, nanospheric polyhydrido copper cluster [Cu20(H)11(S2P(OiPr)2)9] (1H), which is the first example of elongated triangular orthobicupola copper atom array of C3h symmetry, was synthesized and characterized. Its composition is primarily determined by ESI mass spectrometry, and fully characterized by NMR (1H, 2H and 31P), and single crystal X-ray diffraction. The structure of complex 1H can be expressed by a trigonal-bipyramidal unit of [Cu2H5]3- anchored within an elongated triangular orthobicupola polyhedron of eighteen copper atoms, which is further stabilized by eighteen sulphur atoms from nine dithiophosphate ligands and six capping hydrides. The positions of eleven hydrides revealed from the low temperature X-ray diffraction was supported by a density functional theory (DFT) investigation on a simplified model [Cu20H11(S2PH2)9] of C3h symmetry. 1H is capable of releasing H2 gas under irradiation of sunlight, mild thermal condition (at 65 oC), or in the presence of acids at RT.
    Journal of the American Chemical Society 03/2013; 135(12). DOI:10.1021/ja401576s · 11.44 Impact Factor
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    ABSTRACT: Reactions of Ag(I) salt, NH(4)(E(2)P(OR)(2)) (R = (i)Pr, Et; E = Se, S), and NaBH(4) in a 7:6:1 ratio in CH(2)Cl(2) at room temperature, led to the formation of hydride-centered heptanuclear silver clusters, [Ag(7)(H){E(2)P(OR)(2)}(6)] (R = (i)Pr, E = Se (3): R = Et; E = S(4). The reaction of [Ag(10)(E){E(2)P(OR)(2)}(8)] with NaBH(4) in CH(2)Cl(2) produced [Ag(8)(H){E(2)P(OR)(2)}(6)](PF(6)) (R = (i)Pr, E = Se (1): R = Et; E = S(2)), which can be converted to clusters 3 and 4, respectively, via the addition of 1 equiv of borohydride. Intriguingly clusters 1 and 2 can be regenerated via adding 1 equiv of Ag(CH(3)CN)(4)PF(6) to the solution of compounds 3 and 4, respectively. All complexes have been fully characterized by NMR ((1)H, (77)Se, (109)Ag) spectroscopy, UV-vis, electrospray ionization mass spectrometry (ESI-MS), FT-IR, thermogravimetric analysis (TGA), and elemental analysis, and molecular structures of 3(H) and 4(H) were clearly established by single crystal X-ray diffraction. Both 3(H) and 4(H) exhibit a tricapped tetrahedral Ag(7) skeleton, which is inscribed within an E(12) icosahedron constituted by six dialkyl dichalcogenophosphate ligands in a tetrametallic-tetraconnective (μ(2), μ(2)) bonding mode. Density functional theory (DFT) calculations on the models [Ag(7)(H)(E(2)PH(2))(6)] (E = Se: 3'; E = S: 4') yielded to a tricapped, slightly elongated tetrahedral silver skeleton, and time-dependent DFT (TDDFT) calculations reproduce satisfyingly the UV-vis spectrum with computed transitions at 452 and 423 nm for 3' and 378 nm for 4'. Intriguingly further reactions of [Ag(7)(H){E(2)P(OR)(2)}(6)] with 8-fold excess amounts of NaBH(4) produced monodisperse silver nanoparticles with an averaged particle size of 30 nm, which are characterized by scanning electron microscopy (SEM), energy dispersive X-ray (EDX) spectroscopy, X-ray diffraction (XRD), and UV-vis absorption spectrum.
    Inorganic Chemistry 02/2013; 52(4). DOI:10.1021/ic302482p · 4.79 Impact Factor

Publication Stats

2k Citations
657.76 Total Impact Points


  • 1994–2015
    • Université de Rennes 1
      • • Institut des Sciences Chimiques de Rennes (ISCR) - UMR CNRS 6226
      • • UMR CNRS 6118 - Géosciences Rennes
      Roazhon, Brittany, France
  • 2002–2014
    • French National Centre for Scientific Research
      • Institut Néel
      Lutetia Parisorum, Île-de-France, France
    • University of Chile
      • Facultad de Ciencias Químicas y Farmacéuticas
      Santiago, Region Metropolitana de Santiago, Chile
  • 1990–2007
    • Université de Rennes 2
      Roazhon, Brittany, France
  • 2004
    • University of Santiago, Chile
      CiudadSantiago, Santiago Metropolitan, Chile
  • 1996–1997
    • Rice University
      • Department of Chemistry
      Houston, Texas, United States