No abstract

The decomposition of the ruthenium precursor Ru(COD)(COT) (1, COD = 1,5-cyclooctadiene; COT = 1,3,5-cyclooctatriene) in mild conditions (room temperature, 1--3 bar H(2)) in THF leads, in the presence of a stabilizer (polymer or ligand), to nanoparticles of various sizes and shapes. In THF and in the presence of a polymer matrix (Ru/polymer = 5%), crystalline hcp particles of uniform mean size (1.1 nm) homogeneously dispersed in the polymer matrix and agglomerated hcp particles (1.7 nm) were respectively obtained in poly(vinylpyrrolidone) and cellulose acetate. The same reaction, carried out using various concentrations relative to ruthenium of alkylamines or alkylthiols as stabilizers (L = C(8)H(17)NH(2), C(12)H(25)NH(2), C(16)H(33)NH(2), C(8)H(17)SH, C(12)H(25)SH, or C(16)H(33)SH), leads to agglomerated particles (L = thiol) or particles dispersed in the solution (L = amine), both displaying a mean size near 2--3 nm and an hcp structure. In the case of amine ligands, the particles are generally elongated and display a tendency to form worm- or rodlike structures at high amine concentration. This phenomenon is attributed to a rapid amine ligand exchange at the surface of the particle as observed by (13)C NMR. In contrast, the particles stabilized by C(8)H(17)SH are not fluxional, but a catalytic transformation of thiols into disulfides has been observed which involves oxidative addition of thiols on the ruthenium surface. All colloids were characterized by microanalysis, infrared spectroscopy after CO adsorption, high-resolution electron microscopy, and wide-angle X-ray scattering.

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.