Probing the Local Magnetic Structure of the [FeIII(Tp)(CN)3]- Building Block Via Solid-State NMR Spectroscopy, Polarized Neutron Diffraction, and First-Principle Calculations

International audienceThe local magnetic structure in the [Fe (Tp)(CN) ] building block was investigated by combining paramagnetic Nuclear Magnetic Resonance (pNMR) spectroscopy and polarized neutron diffraction (PND) with first-principle calculations. The use of the pNMR and PND experimental techniques revealed the extension of spin-density from the metal to the ligands, as well as the different spin mechanisms that take place in the cyanido ligands Spin-polarization on the carbon atoms and spin-delocalization on the nitrogen atoms. The results of our combined density functional theory (DFT) and multireference calculations were found in good agreement with the PND results and the experimental NMR chemical shifts. Moreover, the ab-initio calculations allowed us to connect the experimental spin-density map characterized by PND and the suggested distribution of the spin-density on the ligands observed by NMR spectroscopy. Interestingly, significant differences were observed between the pseudo-contact contributions of the chemical shifts obtained by theoretical calculations and the values derived from NMR spectroscopy using a simple point-dipole model. These discrepancies underline the limitation of the point-dipole model and the need for more elaborate approaches to break down the experimental pNMR chemical shifts into contact and pseudo-contact contributions

Polarized Neutron Diffraction: An Excellent Tool to Evidence the Magnetic Anisotropy—Structural Relationships in Molecules

This publication reviews recent advances in polarized neutron diffraction (PND) studies of magnetic anisotropy in coordination compounds comprising d or f elements and having different nuclearities. All these studies illustrate the extent to which PND can provide precise and direct information on the relationship between molecular structure and the shape and axes of magnetic anisotropy of the individual metal sites. It makes this experimental technique (PND) an excellent tool to help in the design of molecular-based magnets and especially single-molecule magnets for which strong uniaxial magnetic anisotropy is required

Joint Refinement of Charge and Spin Densities

International audienceA new charge and spin density model and the corresponding refinement software were recently developed to combine X- ray and polarized neutron diffraction experiments [1]. This joint refinement procedure allows getting access to both charge and spin densitiy distributions by refining both spin up and down parameters for magnetic atoms. The paper is focused on the refinement procedure and its application to the case of an end-to-end azido double bridged copper(II) complex. The results of this joint refinement of X-ray and polarized neutron diffraction data are presented

Spin delocalization in the molecular manganese tetra-helicate cluster: [Mn3L4](ClO4)2(H2O)2

The magnetic properties of the compound [Mn3L4](C1O4)2(H2O)2 revealed that it is a rare trinuclear MnII compound showing ferromagnetic interactions and a possible anisotropic behaviour. Here we report preliminary magnetic susceptibility measurements and spin density determinations at the Mn and O atoms to elucidate the magnetic interaction model and the possible anomalous anisotropic magnetic behaviour reported previously for this compound, that it is confirmed to be inexistent.This work has been funded by the Spanish MICINN and FEDER, Projects MAT2007-61621, MAT2009-13977-C03-01, and CSD2007-00010. C Rodríguez-Blanco acknowledges the “Europe Program” of CAI and Aragón Government for financial support.Peer Reviewe

Experimental and theoretical study of the spin ground state of the high-spin 3 molecular cluster [NiII{NiII(CH3OH)3}8(l-CN)30{WV(CN)3}6] 15CH3OH by 4 polarised neutron diffraction and density functional theory calculatio

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Light-induced phase separation in the [Fe(ptz)6](BF4)2 spin-crossover single crystal

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Individual-collective crossover driven by particle size in dense assemblies of superparamagnetic nanoparticles

International audiencePrussian blue analogues (PBA) ferromagnetic nanoparticles Cs I x Ni II [Cr III (CN)6 ] z ·3(H2O) embedded in CTA+ (cetyltrimethylammonium) matrix have been investigated by magnetometry and magnetic small-angle neutron scattering (SANS). Choosing particle sizes (diameter D = 4.8 and 8.6 nm) well below the single-domain radius and comparable volume fraction of particle, we show that the expected superparamagnetic regime for weakly anisotropic isolated magnetic particles is drastically affected due to the interplay of surface/volume anisotropies and dipolar interactions. For the smallest particles (D = 4.8 nm), magnetocrystalline anisotropy is enhanced by surface spins and drives the system into a regime of ferromagnetically correlated clusters characterized by a temperature-dependent magnetic correlation length L mag which is experimentally accessible using magnetic SANS. For D = 8.6 nm particles, a superparamagnetic regime is recovered in a wide temperature range. We propose a model of interacting single-domain particles with axial anisotropy that accounts quantitatively for the observed behaviors in both magnetic regimes

Small-angle neutron scattering study of the short-range organization of dispersed CsNi[Cr(CN) 6 ] nanoparticles

International audiencePrussian blue analogues magnetic nanoparticles (of radius R0 = 2.4–8.6 nm) embedded in PVP (polyvinylpyrrolidone) or CTA+ (cetyltrimethylammonium) matrices have been studied using neutron diffraction and small angle neutron scattering (SANS) at several concentrations. For the most diluted particles in neutral PVP, the SANS signal is fully accounted for by a “single-particle” spherical form factor with no structural correlations between the nanoparticles and with radii comparable to those inferred from neutron diffraction. For higher concentration in PVP, structural correlations modify the SANS signal with the appearance of a structure factor peak, which is described using an effective “mean-field” model. A new length scale R* ≈ 3R0, corresponding to an effective repulsive interaction radius, is evidenced in PVP samples. In CTA+, electrostatic interactions play a crucial role and lead to a dense layer of CTA+ around the nanoparticles, which considerably alter the SANS patterns as compared to PVP. The SANS data of nanoparticles in CTA+ are best described by a core-shell model without visible inter-particle structure factor

Les rayon X et les neutrons se combinent pour révéler la densité résolue en spin

International audienceLa distribution des électrons dans un cristal peut être reconstruite avec une grande précision au moyen de la diffraction des rayons X à haute résolution, alors que la diffraction des neutrons polarisés en spin permet de retrouver la densité d’aimantation. Bien que les grandeurs ainsi mesurées soient toutes deux une traduction du comportement des électrons, ces deux types d’expérience de diffusion sont de nos jours interprétées par des modèles différents.Nous retraçons ici les étapes ayant conduit à la première détermination expérimentale de la densité d’électrons résolue en spin par un traitement combiné des données de diffraction de rayons X et de neutrons polarisés

An unique model for joint refinement of (polarised) neutron and X-ray data

International audienceA new charge and spin density model and the corresponding refinement software were recently developed to combine X-ray and polarised neutron diffraction experiments [1,2]. This joint refinement procedure allows for an access to both the charge and spin densities but also to spin up ( ) and spin down ( ) electron distributions. These two quantities ( and ) were thus separately modelled and for the first time it was possible to compare them with theoretical results. The first part of the presentation will introduce the refinement procedure and describe its application to the case of an end-to-end azido double bridged copper(II) complex[3]. The results of this joint refinement of X-ray and polarized neutron diffraction data will be compared to theoretical calculations. The second part will be devoted to recent applications to other materials including a purely organic radical