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Bruno Chaudret

Publications and source records attributed to Bruno Chaudret.

At least 19 recordsLinked to original sources
PubMed2006

Optical properties of zinc oxide nanoparticles and nanorods synthesized using an organometallic method.

The emission properties of nanocrystalline ZnO particles prepared following an organometallic synthetic method are investigated. Spherical particles and nanorods are studied. The shape of the particles and the ligands used are shown to influence the luminescence properties in the visible domain. Two different emissions are observed at 440 nm (approximately 2.82 eV) and at 580 nm (approximately 2.14 eV) that are associated with the presence of surface defects on the particles. The first emission corresponds to the well-known yellow emission located at 580 nm (approximately 2.14 eV) with a lifetime of 1850 ns for 4.0 nm size ZnO nanoparticles. The second emission at 440 nm (approximately 2.82 eV) is observed when amine functions are present. This strong blue emission is associated with an excitation energy less than that associated with the yellow emission displaying a lifetime of nine nanoseconds. A possible hole trapping effect by the amine groups on the surface of the ZnO particles is discussed as the origin of this emission. The modification of the intensities between the two visible emissions for different particle shapes is proposed to be related to a specific location of the amine ligands on the surface of the particles.

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PubMed2006

Novel insights into the mechanism of the ortho/para spin conversion of hydrogen pairs: implications for catalysis and interstellar water.

The phenomenon of exchange coupling is taken into account in the description of the magnetic nuclear spin conversion between bound ortho- and para-dihydrogen. This conversion occurs without bond breaking, in contrast to the chemical spin conversion. It is shown that the exchange coupling needs to be reduced so that the corresponding exchange barrier can increase and the given magnetic interaction can effectively induce a spin conversion. The implications for related molecules such as water are discussed. For ice, a dipolar magnetic conversion and for liquid water a chemical conversion are predicted to occur within the millisecond timescale. It follows that a separation of water into its spin isomers, as proposed by Tikhonov and Volkov (Science 2002, 296, 2363), is not feasible. Nuclear spin temperatures of water vapor in comets, which are smaller than the gas-phase equilibrium temperatures, are proposed to be diagnostic for the temperature of the ice or the dust surface from which the water was released.

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PubMed2005

Synthesis, neutron structure, and reactivity of the bis(dihydrogen) complex RuH2(eta(2)-H2)2(PCyp3)2 stabilized by two tricyclopentylphosphines.

Treatment of Ru(eta4-C8H12)(eta6-C8H10) with 3 bar H2 in the presence of 2 equiv of tricyclopentylphosphine (PCyp3) in pentane resulted in the isolation of the new bis(dihydrogen) complex RuH2(eta2-H2)2(PCyp3)2 (2), characterized by NMR and single-crystal X-ray and neutron diffraction. The single-crystal neutron diffraction study is the first carried out for a bis(dihydrogen) complex. The coordination geometry around the metal center is a distorted octahedron defined by the two phosphines in a trans configuration (making an angle of 168.9(1) degrees ), two cis dihydrogen ligands, and two hydrides trans to them, defining the equatorial plane. The H-H bond distances (0.825(8) and 0.835(8) A) are characteristic of two "unstretched" dihydrogen ligands. H/D exchange between the Ru-H and the C-D bonds of deuterated benzene is observed within 1 h, leading to the formation of various isotopomers RuHxD6-x(PCyp3)2 (with x = 0-6). 2 is a catalyst precursor for ethylene coupling (20 bar, 293 K) to a functionalized arene (Murai reaction). We found a 90% conversion of acetophenone to 2-ethylacetophenone within 35 min, whereas 10 h was needed in the same conditions using the analogous tricyclohexylphosphine complex, RuH2(eta2-H2)2(PCy3)2, the best catalyst precursor, at room temperature, prior to this work.

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PubMed2005

Multimillimetre-large superlattices of air-stable iron-cobalt nanoparticles.

Self-organization of nanoparticles into two- and three-dimensional superlattices on a large scale is required for their implementation into nano- or microelectronic devices. This is achieved, generally after a size-selection process, through spontaneous self-organization on a surface, layer-by-layer deposition or the three-layer technique of oversaturation, but these techniques consider superlattices of limited size. An alternative method developed in our group involves the direct formation in solution of crystalline superlattices, for example of tin nanospheres, iron nanocubes or cobalt nanorods, but these are also of limited size. Here, we report the first direct preparation in solution of multimillimetre-sized three-dimensional compact superlattices of nanoparticles. The 15-nm monodisperse FeCo particles adopt an unusual short-range atomic order that transforms into body-centred-cubic on annealing at 500 degrees C. The latter process produces an air-stable material with magnetic properties suitable for radiofrequency applications.

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PubMed2005

The solid-state synthesis of metal nanoparticles from organometallic precursors.

Nanoparticles (NPs), average size of 2-5 nm, of ruthenium, cobalt, and rhodium have been prepared by an original method, namely the solid-state decomposition under dihydrogen of an organometallic precursor either dispersed in polymer films or directly as nanocrystals. The NPs dispersion, size, and morphology are investigated by transmission electron microscopy, and their structure by wide angle X-ray scattering. Infrared spectroscopy, after adsorption of carbon monoxide on the metal NPs surfaces, evidences a nonoxidized surface of high reactivity.

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PubMed2004

Bridging the gap between homogeneous and heterogeneous catalysis: ortho/para H(2) conversion, hydrogen isotope scrambling, and hydrogenation of olefins by Ir(CO)Cl(PPh(3))(2).

Some transition metal complexes are known to catalyze ortho/para hydrogen conversion, hydrogen isotope scrambling, and hydrogenation reactions in liquid solution. Using the example of Vaska's complex, we present here evidence by NMR that the solvent is not necessary for these reactions to occur. Thus, solid frozen solutions or polycrystalline powdered samples of homogeneous catalysts may become heterogeneous catalysts. Comparative liquid- and solid-state studies provide novel insight into the reaction mechanisms.

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PubMed2004

A case for enantioselective allylic alkylation catalyzed by palladium nanoparticles.

Palladium nanoparticles (4 nm, fcc) were prepared through decomposition of [Pd2(dba)3] by H2 in the presence of a chiral xylofuranoside diphosphite. These particles catalyze the allylic alkylation of rac-3-acetoxy-1,3-diphenyl-1-propene with dimethyl malonate leading to an almost total conversion of the (R) enantiomer and almost no reaction with the (S). This gives rise to 97% ee for the alkylation product and a kinetic resolution of the substrate recovered with ca. 90% ee. This behavior was compared to that of a molecular catalyst at various dilutions, and the differences between the two systems are discussed. This is the first colloidal system shown to display such a high enantioselectivity besides the well-known Pt/cinchonidine system.

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PubMed2004

Superlattices of iron nanocubes synthesized from Fe[N(SiMe3)2]2.

The reaction of the metal-organic precursor Fe[N(SiMe3)2]2 with H2 in the presence of a long-chain acid and a long-chain amine in various proportions produces monodisperse zerovalent iron nanoparticles. These Fe particles display magnetic properties that match those of bulk iron as evidenced by magnetic and Mössbauer measurements. The nanoparticles adopt a cubic shape with edges of 7 nanometers and are incorporated into extended crystalline superlattices containing nanocubes in close proximity and with their crystallographic axes aligned. These superlattices are formed in solution, precipitate in high yield, and may be redissolved and redeposited as two-dimensional arrays.

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PubMed2004

Magnetic nanoparticles through organometallic synthesis: evolution of the magnetic properties from isolated nanoparticles to organised nanostructures.

Co and NiFe nanoparticles (2.7 to 3.3 nm mean diameter) of narrow size distribution have been obtained through the decomposition of organometallic precursors in organic solutions of long alkyl chain ligands, namely oleic acid and hexadecylamine. Materials of various volume fractions were produced. The particles have been structurally characterised by WAXS. Both adopt the bulk structure: HCP in the case of cobalt; a mixture of FCC and BCC for NiFe. Their aptitude to self-assemble either on flat supports or in bulk solid state has been investigated by means of TEM and SAXS. This study suggests the crystallisation of the nanoparticles upon solvent evaporation, especially a local FCC arrangement was observed for the NiFe material. Magnetic measurements (SQUID) confirm this tendency. The blocking temperature depends on the metal volume fraction, i.e. on the anisotropy generated by the dipolar couplings (Ki). We show that, for dense samples, the particles of high intrinsic anisotropy, Ku, (Co) still display an individual behaviour while the soft ones (NiFe) display a collective behaviour.

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PubMed2003

Ruthenium dihydrogen complexes with wide bite angle diphosphines.

The wide bite angle diphosphines homoxantphos (10,11-dihydro-4,5,-bis(diphenylphosphino)dibenzo[b,f]oxepine), sixantphos (4,6-bis(diphenylphosphino)-10,10-dimethylphenoxasilin), and thixantphos (2,8-dimethyl-4,6-bis(diphenylphosphino)phenoxathiin) were used to prepare cis[MH(2)(diphosphine)(2)] complexes (1a-f) by reaction of [Ru(cod)(cot)] (cod = cyclo-octa-1,5-diene, cot = cyclo-octa-1,3,5-triene) with 2 equiv of the diphosphine under dihydrogen pressure. The electronic properties of the thixantphos ligand were varied. Complexes 1a-f can be protonated with HBF(4) or CF(3)COOH to yield hydrido(dihydrogen) complexes cis[MH(H(2))(diphosphine)(2)](+) (2a-f), which were characterized by VT (variable temperature) NMR and T(1) measurements. These complexes show fast hydrogen atom exchange between the eta(2)-H(2) and the terminal hydride at all temperatures studied. They are thermally unstable toward dihydrogen loss yielding the cationic monohydride complexes cis[MH(diphosphine)(2)](+) (3a-f). Coordination of the eta(2)-H(2) is dominated by sigma --> d donation, and hence, the H-H distance is hardly influenced by the electronic properties of the ligands.

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PubMed2002

Magnetic enhancement in nanoscale CoRh particles.

The influence of size reduction on the magnetism of CoRh has been studied on a system of isolated nanometric spherical bimetallic ultrafine particles embedded in a polymer matrix. Pulsed fields up to 30 T were used in order to approach the magnetic saturation ( M(S)). Particles with a mean diameter of 1.65 (+/-0.1) nm display a value of 2.38 micro(B) per CoRh unit strongly enhanced compared to values calculated or measured on a bulk alloy. These results were interpreted as the first evidence of the cooperative role of both alloying and size reduction to the enhancement of M(S) in this system associating a 3d FM metal with a 4d metal.

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