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[Fe.sub.x][Rh.sub.100-x] (x = 50, 80) nanoparticles (NPs) with an average diameter of ~2 nm were prepared by simultaneous decomposition of stoichiometric quantities of Fe[[N[(Si[([CH.sub.3]).sub.3]).sub.2])].sub.2] and Rh[([C.sub.3][H.sub.5]).sub.3] using two different routes: 1) a standard hydrogenation procedure and 2) a new one based on use of amino-borane as a reducing agent. All samples were found to be superparamagnetic with a blocking temperature below 10 K. Results of X-Ray magnetic circular dichroism (XMCD) experiments at the Fe K-edge and the Rh [L.sub.2,3] edges have shown that not only iron but also rhodium atoms are magnetic as a result of hybridization of Fe 3d states with 4d states of Rh. The total induced magnetic moment of Rh atoms as well as its spin and orbital contributions are shown to depend on chemical composition of [NP.sub.S] and the preparation method. Index Terms--Induced magnetic moment, magnetic nanoparticles, X-ray magnetic circular dichroism.

A variety of imaging technologies are now routinely used in the medical field, their use being continuously enlarged through the development of contrast agents. Recently nanoparticles (NPs) proved efficient to improve imaging in vivo by increasing contrast and targeting capabilities. The current trend is now focused on the development of dual contrast agents combining two or more functionalities on the same NP. Motivated by this new challenge we developed FeBi NPs as new nanomaterials with potential application as a contrast agent for MRI and CT imaging. In addition to the well-known use of iron in the development MRI contrast agents, we chose Bi as a CT imaging agent rather than the more documented gold, because it possesses a larger X-ray attenuation coefficient and is much less expensive. Two sets of NPs, with sizes around 150 nm and 14 nm, were synthesized using organometallic approaches. In both cases, the NPs are spherical, and contain distinct domains of Fe and Bi, with the surface being enriched with Fe, and a hydrophobic coating. This coating differs from one sample to the other: the surfaces of the 150 nm large NPs are coated by amine ligands, while those of the 14 nm large NPs are coated by a mixture of an amine and its hydrochloride salt. Exchange of the surface ligands to afford water soluble NPs has been attempted. We show that only the larger NPs could be functionalized with water soluble ligands, which is in agreement with the lability of their initial surface coating. Colloidal aqueous solutions of FeBi NPs with glycoPEG ligands have been obtained. [ABSTRACT FROM AUTHOR]

Cobalt nanoparticles with different sizes and morphologies including spheres, rods, disks, and hexagonal prisms have been synthesized through the decomposition of the olefinic precursor [Co(η(3)-C8H13)(η(4)-C8H12)] under dihydrogen, in the presence of hexadecylamine and different rhodamine derivatives, or aromatic carboxylic acids. UV-vis spectroscopy, X-ray diffraction, low and high resolution transmission electron microscopy, and electron tomography have been used to characterize the nanomaterials. Especially, the Co nanodisks formed present characteristics that make them ideal nanocrystals for applications such as magnetic data storage. Focusing on their growth process, we have evidenced that a reaction between hexadecylamine and rhodamine B occurs during the formation of these Co nanodisks. This reaction limits the amount of free acid and amine, usually at the origin of the formation of single crystal Co rods and wires, in the growth medium of the nanocrystals. As a consequence, a growth mechanism based on the structure of the preformed seeds rather than oriented attachment or template assisted growth is postulated to explain the formation of the nanodisks.

The effectiveness of amine-borane as reducing agent for the synthesis of iron nanoparticles has been investigated. Large (2-4 nm) Fe nanoparticles were obtained from [Fe{N(SiMe3)2}2]. Inclusion of boron in the nanoparticles is clearly evidenced by extended X-ray absorption fine structure spectroscopy and Mössbauer spectrometry. Furthermore, the reactivity of amine-borane and amino-borane complexes in the presence of pure Fe nanoparticles has been investigated. Dihydrogen evolution was observed in both cases, which suggests the potential of Fe nanoparticles to promote the release of dihydrogen from amine-borane and amino-borane moieties., (Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

We investigate the formation of bi-metallic particles in the Fe-Bi system, well known as totally immiscible in the bulk, using a large combination of structural and element-sensitive techniques, well-adapted to the nanoscale. The synthesis approach makes use of the kinetics of decomposition of the different precursors to achieve a controlled sequential growth of the different elements. Different ligands have also been used in order to limit the size and ensure dispersion of the synthesized particles. Our results give evidence for the presence of body-centered cubic ferromagnetic iron nanograins together with larger bismuth crystallites. Interestingly, while the iron particles remain very small, the resistance to oxidation of the Fe-Bi nanocomposites highly depends on the stabilizing ligand used in the synthesis. The presence of both metals, Fe and Bi, in a single cluster has been clearly revealed in the oxidation resistant composite synthesized using the HMDS ligand.

A novel cascade of reactions is designed to control in situ the deposition of noble metal islands (e.g. Rh) on top of nanoparticles of a 3d metal (e.g. Fe, Co).

Polytetrahedral NiFe nanoparticles with diameters of (2.8+/-0.3) nm have been obtained by hydrogenation of Ni[(COD)(2)] (COD=1,5-cyclooctadiene) and Fe[{N(SiMe(3))(2)}(2)] at 150 degrees C using stearic acid and hexadecylamine as stabilizing ligands. The nanoparticles are superparamagnetic at room temperature and display a blocking temperature of 17.6 K. Their anisotropy (2.7x10(5)J m(-3)) is determined to be more than two orders of magnitude higher than that of the bulk NiFe alloy (10(3)J m(-3)) and is close to that determined for Fe nanoparticles of the same size. Still, they display a magnetization of (1.69+/-0.05) mu(B) per metallic atom, identical to that of the bulk NiFe alloy. Combining the results from X-ray absorption and Mössbauer studies, we evidence a progressive enrichment in iron atoms from the core to the surface of the nanoparticles. These results are discussed in relation to both size and chemical effects. They show the main role played by the enriched Fe surface on the magnetic properties and address the feasibility of soft magnetic materials at the nanoscale.