79 research outputs found
Cantilever torque magnetometry: a powerful tool to investigate magnetic anisotropy in crystals and thin films.
Commentary on "An intermediate state between the kagome-ice and the fully polarized state in DyTiO"
A Commentary on the paper by S A Grigera et al. [Pap. Phys. 7, 070009 (2015)].
Received: 25 June 2015, Accepted: 25 June 2015; Edited by: A. Vindigni; DOI: http://dx.doi.org/10.4279/PIP.070010
Cite as: M Perfetti, Papers in Physics 7, 070010 (2015
Relaxation Dynamics and Magnetic Anisotropy in a Low-Symmetry DyIII Complex
The magnetic behaviour of a Dy(LH)3 complex (LH(-) is the anion of 2-hydroxy-N'-[(E)-(2-hydroxy-3-methoxyphenyl)methylidene]benzhydrazide) was analysed in depth from both theoretical and experimental points of view. Cantilever torque magnetometry indicated that the complex has Ising-type anisotropy, and provided two possible directions for the easy axis of anisotropy due to the presence of two magnetically non-equivalent molecules in the crystal. Ab initio calculations confirmed the strong Ising-type anisotropy and disentangled the two possible orientations. The computed results obtained by using ab initio calculations were then used to rationalise the composite dynamic behaviour observed for both pure Dy(III) phase and Y(III) diluted phase, which showed two different relaxation channels in zero and non-zero static magnetic fields. In particular, we showed that the relaxation behaviour at the higher temperature range can be correctly reproduced by using a master matrix approach, which suggests that Orbach relaxation is occurring through a second excited doublet
Tris‐{hydridotris(1‐pyrazolyl)borato}actinide Complexes: Synthesis, Spectroscopy, Crystal Structure, Bonding Properties and Magnetic Behaviour
The isostructural compounds of the trivalent actinides uranium, neptunium, plutonium, americium, and curium with the hydridotris(1-pyrazolyl)borato (Tp) ligand An[η-HB(NCH)] (AnTp) have been obtained through several synthetic routes. Structural, spectroscopic (absorption, infrared, laser fluorescence) and magnetic characterisation of the compounds were performed in combination with crystal field, density functional theory (DFT) and relativistic multiconfigurational calculations. The covalent bonding interactions were analysed in terms of the natural bond orbital (NBO) and quantum theory of atoms in molecules (QTAIM) models
Tris‐{hydridotris(1‐pyrazolyl)borato}actinide Complexes: Synthesis, Spectroscopy, Crystal Structure, Bonding Properties and Magnetic Behaviour
The isostructural compounds of the trivalent actinides uranium, neptunium, plutonium, americium, and curium with the hydridotris(1-pyrazolyl)borato (Tp) ligand An[η-HB(NCH)] (AnTp) have been obtained through several synthetic routes. Structural, spectroscopic (absorption, infrared, laser fluorescence) and magnetic characterisation of the compounds were performed in combination with crystal field, density functional theory (DFT) and relativistic multiconfigurational calculations. The covalent bonding interactions were analysed in terms of the natural bond orbital (NBO) and quantum theory of atoms in molecules (QTAIM) models
Single Crystal Investigations Unravel the Magnetic Anisotropy of the “Square-In Square” Cr₄Dy₄ SMM Coordination Cluster
Single Crystal Investigations Unravel the Magnetic Anisotropy of the “Square-In Square” Cr4Dy4 SMM Coordination Cluster
In the search for new single molecule magnets (SMM), i.e., molecular systems that can retain their magnetization without the need to apply an external magnetic field, a successful strategy is to associate 3d and 4f ions to form molecular coordination clusters. In order to efficiently design such systems, it is necessary to chemically project both the magnetic building blocks and the resultant interaction before the synthesis. Lanthanide ions can provide the required easy axis magnetic anisotropy that hampers magnetization reversal. In the rare examples of 3d/4f SMMs containing CrIII ions, the latter turn out to act as quasi-isotropic anchors which can also interact via 3d-4f coupling to neighbouring Ln centres. This has been demonstrated in cases where the intramolecular exchange interactions mediated by CrIII ions effectively reduce the efficiency of tunnelling without applied magnetic field. However, describing such high nuclearity systems remains challenging, from both experimental and theoretical perspectives, because the overall behaviour of the molecular cluster is heavily affected by the orientation of the individual anisotropy axes. These are in general non-collinear to each other. In this article, we combine single crystal SQUID and torque magnetometry studies of the octanuclear [Cr4Dy4(μ3-OH)4(μ-N3)4(mdea)4(piv)8]·3CH2Cl2 single molecule magnet (piv=pivalate and mdea=N-methyldiethanol amine). These experiments allowed us to probe the magnetic anisotropy of this complex which displays slow magnetization dynamics due to the peculiar arrangement of the easy-axis anisotropy on the Dy sites. New ab initio calculations considering the entire cluster are in agreement with our experimental results
Chemical tunnel-splitting-engineering in a dysprosium-based molecular nanomagnet
Total control over the electronic spin relaxation in molecular nanomagnets is the ultimate goal in the design of new molecules with evermore realizable applications in spin-based devices. For single-ion lanthanide systems, with strong spin-orbit coupling, the potential applications are linked to the energetic structure of the crystal field levels and quantum tunneling within the ground state. Structural engineering of the timescale of these tunneling events via appropriate design of crystal fields represents a fundamental challenge for the synthetic chemist, since tunnel splittings are expected to be suppressed by crystal field environments with sufficiently high-order symmetry. Here, we report the long missing study of the effect of a non-linear (C4) to pseudo-linear (D4d) change in crystal field symmetry in an otherwise chemically unaltered dysprosium complex. From a purely experimental study of crystal field levels and electronic spin dynamics at milliKelvin temperatures, we demonstrate the ensuing threefold reduction of the tunnel splitting.M.A.S., U.B.H., K.L., and J.Be. acknowledge financial support from the Danish Research Councils for Independent Research (12-125226). M.A.S., U.B.H., M.R, and K.L. acknowledge DANSCATT for financial support for the neutron scattering experiments. For the experiments conducted at FRM II, this project has received funding from the European Union’s 7th Framework Programme for research, technological development and demonstration under the NMI3-II Grant number 283883. M.A.S. thanks the Oticon Foundation (16-2669), and the Augustinus Foundation (16-2917) for financial support in relation to a research stay at Institut für Physikalische Chemie, Universität Stuttgart, Germany. M.P. and J.v.S. thank the DFG for funding (SL104/5-1). K.S.P. thanks the Danish Research Council for Independent Research for a DFF-Sapere Aude Research
Talent grant (4090-00201). E.B., A.A, and, J.Ba. acknowledge the financial support of Spanish MINECO project MAT2017-83468-R. M.J. acknowledges the Swiss National Science Foundation.Peer reviewe
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