The fine control of iron oxide nanocrystal sizes within the nanometre scale (diameters range from 2.5 to 14 nm) allows us to investigate accurately the size-dependence of their structural and magnetic properties. A study of the growth conditions of these nanocrystals obtained by thermal decomposition of an iron oleate precursor in high-boiling point solvents has been carried out. Both the type of solvent used and the ligand/precursor ratio have been systematically varied, and were found to be the key parameters to control the growth process. The lattice parameters of all the nanocrystals deduced from X-ray diffraction measurements are consistent with a structure of the type Fe3-xO4, i.e. intermediate between magnetite and maghemite, which evolves toward the maghemite structure for the smallest sizes (x=1/3). The evolution of the magnetic behavior with nanoparticle sizes emphasizes clearly the influence of the surface, especially on the saturation magnetization Ms and the magneto-crystalline anisotropy K. Dipolar interactions and thermal dependence have been also taken into account in the study on the nanoscale size-effect of magnetic properties.

Most studies on the synthesis of nanoparticles are currently focused on the controlled synthesis of new morphologies, including core-shell structures, which are expected to exhibit new magnetic properties for uses in spintronics and recording media applications. In this study, the structure, morphology, and composition of cubic-shaped nanoparticles are carefully investigated and compared to those of spherically shaped nanoparticles through the use of a combination of techniques: X-ray diffraction (XRD) and transmission electronic microscopy (TEM) combined with more sensitive techniques such as scanning transmission electron microscopy-high-angle annular dark field (STEM-HAADF) imaging, electron tomography, and holography. While spherically shaped nanoparticles (NPs) crystallize with the spinel structure, cubic-shaped NPs can be described as a cubic core of w€ ustite surrounded by a spinel shell. Stresses are observed at the core-shell interface and within the spinel shell due to the epitaxial growth and oxidation mechanisms of the w€ ustite phase. Furthermore, magnetic measurements displayed an exchange bias coupling between the antiferromagnetic (AFM) core and the ferrimagnetic (FIM) shell structure of cubic-shaped nanoparticles. It is shown that the magnetic properties are influenced by stresses generated by the oxidation of w€ ustite and, also exhibit variations depending upon the evolution of this core-shell structure as a function of the oxidation time.

A systematic study of Co(SiO 2 ) granular films by means of transmission electron microscopy ͑TEM͒, dc and ac initial magnetic susceptibility, and thermoremanent magnetization ͑TRM͒ is presented. The experimental results are compared with simulations of zero-field-cooled ͑ZFC͒ and field-cooled ͑FC͒ magnetization and TRM curves obtained using a simple model of noninteracting nanoparticles. The simulated ZFC/FC curves, using the actual parameters obtained from the TEM images, show a different behavior than the experimental magnetic data. The effect of the dipolar interaction among particles introduces a self-averaging effect over a correlation length ⌳, which results in a larger average ''magnetic'' size of the apparent particles together with a narrower size distribution. The analysis of the ZFC/FC curves in the framework of independent ''particle clusters'' of volume ⌳ 3 , involving about 25 real particles, explains very well the observed difference between the experimental data for the median blocking temperature ͗T B ͘ and their distribution width with respect to the ones expected from the structural observations by TEM. The experimental TRM curves also differ from those obtained from the theoretical model, starting to decrease at a lower temperature than expected from the model, also indicating the strong influence of dipole-dipole interactions.

A new terephthalate-based cobalt hydroxide, Co 2 (OH) 2 (C 8 H 4 O 4 ), was synthesized by the hydrothermal method. Its crystal structure has been determined by ab-initio XRPD methods (monoclinic, C2/m, a ) 19.943(1), b ) 3.2895(1), c ) 6.2896(3) Å, β ) 95.746(3)°) and fully refined by the Rietveld technique down to R p ) 0.15 for 9301 observed data (178 independent reflections). The terephthalates are coordinated and pillared directly to the cobalt hydroxide layers and thus a three-dimensional framework is formed. Because of the bonds with the terephthalates, two crystallographically inequivalent cobalt sites are found inside the hydroxide layers, with different octahedral orientations. Magnetic studies show that the intralayer exchange interaction between Co(II) ions is ferromagnetic but the whole system orders antiferromagnetically at 48 K with a metamagnetic transition above a threshold field of 0.2 T. The existence of conjugated π electrons in terephthalates explains the antiferromagnetic interactions between the layers. Below 45 K, the compound exhibits a hysteretic metamagnetic loop and a remnant moment that is small down to about 30 K, and then rises suddenly reaching a plateau below 15 K. However, at low temperatures the remnant moment is still only a fraction of the full Co(II) moment, which is a sign of canted antiferromagnetism associated with a non-collinear orientation of the moments between the layers. The magnetization loop shows a giant coercive field of 5.9 T at 4.2 K, which must be related to an extremely large single-ion anisotropy on the Co sites.

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Octahedral Co(2+) centers have been connected by mu(3)-OH and mu(2)-OH(2) units forming [Co(4)] clusters which are linked by pyrazine forming a two-dimensional network. The two-dimensional layers are bridged by oxybisbenzoate (OBA) ligands giving rise to a three-dimensional structure. The [Co(4)] clusters bond with the pyrazine and the OBA results in a body-centered arrangement of the clusters, which has been observed for the first time. Magnetic studies reveal a noncollinear frustrated spin structure of the bitriangular cluster, resulting in a net magnetic moment of 1.4 microB per cluster. For T > 32 K, the correlation length of the cluster moments shows a stretched-exponential temperature dependence typical of a Berezinskii-Kosterlitz-Thouless model, which points to a quasi-2D XY behavior. At lower temperature and down to 14 K, the compound behaves as a soft ferromagnet and a slow relaxation is observed, with an energy barrier of ca. 500 K. Then, on further cooling, a hysteretic behavior takes place with a coercive field that reaches 5 T at 4 K. The slow relaxation is assigned to the creation/annihilation of vortex-antivortex pairs, which are the elementary excitations of a 2D XY spin system.

The influence of pressure on the structure and magnetic properties of the layered hybrid compounds Cu 2 (OH) 3 (n-C m H 2mϩ1 CO 2 )•zH 2 O is investigated for mϭ10 and 12. It is shown that the distance between magnetic copper͑II͒ layers, up to 40.7 Å, is not significantly modified and that the temperature of the ferromagnetic ordering decreases linearly with pressure increase. We present a new analysis of the susceptibility data, based on the scaling theory of phase transitions, which clearly shows up a crossover from a hightemperature two-dimensional ͑2D͒ behavior to a 3D regime at about 30 K, around 10 K above the long-range ordering temperature. A model of quantum ferromagnetic layers interacting through dipolar coupling, taking into account the temperature dependence of correlated spin domains in a mean-field approach, allows us to explain the stabilization of a 3D order at a T C value very close to that observed experimentally. The decrease of T C under pressure is shown to be mainly driven by the decrease of in-plane interactions, which can be caused by small variations of the Cu-O-Cu bond angles within the layer.