Javier Luzón

Lanthanides in molecular magnetism: so fascinating, so challenging.

Due to their usual large magnetic moments and large magnetic anisotropy lanthanide ions are investigated for the search of Single Molecule Magnets with high blocking temperature. However, the low symmetry crystal environment, the complexity of the electronic states or the non-collinearity of the magnetic anisotropy easy-axes in polynuclear systems make the rationalization of the magnetic behaviour of lanthanide based molecular systems difficult. In this perspective article we expose a methodology in which the use of additional characterization techniques, like single crystal magnetic measurements or luminescence experiments, complemented by relativistic ab initio calculations and a suitable choice of spin Hamiltonian models, can be of great help in order to overcome such difficulties, representing an essential step for the rational design of lanthanide based Single Molecule Magnets with enhanced physical properties.

Magnetic Anisotropy and Spin‐Parity Effect Along the Series of Lanthanide Complexes with DOTA

Spotting trends: Upon going from Tb(III) to Yb(III) centers in the complexes of the DOTA(4-) ligand, a reorientation of the easy axis of magnetization from perpendicular to parallel to the Ln-O bond of the apical water molecule is experimentally observed and theoretically predicted (SMM=single-molecule magnet). Only ions with an odd number of electrons show slow relaxation of the magnetization.

Magnetic Anisotropy of Dysprosium(III) in a Low-Symmetry Environment: A Theoretical and Experimental Investigation

A mixed theoretical and experimental approach was used to determine the local magnetic anisotropy of the dysprosium(III) ion in a low-symmetry environment. The susceptibility tensor of the monomeric species having the formula [Dy(hfac)(3)(NIT-C(6)H(4)-OEt)(2)], which contains nitronyl nitroxide (NIT-R) radicals, was determined at various temperatures through angle-resolved magnetometry. These results are in agreement with ab initio calculations performed using the complete active space self-consistent field (CASSCF) method, validating the predictive power of this theoretical approach for complex systems containing rare-earth ions, even in low-symmetry environments. Susceptibility measurements performed with the applied field along the easy axis eventually permitted a detailed analysis of the temperature and field dependence of the magnetization, providing evidence that the Dy ion transmits an antiferromagnetic interaction between radicals but that the Dy-radical interaction is ferromagnetic.

Spin Chirality in a Molecular Dysprosium Triangle: The Archetype of the Noncollinear Ising Model

Single crystal magnetic studies combined with a theoretical analysis show that cancellation of the magnetic moments in the trinuclear Dy3+ cluster [Dy{3}(mu{3}-OH)2L3Cl(H2O){5}]Cl{3}, resulting in a nonmagnetic ground doublet, originates from the noncollinearity of the single-ion easy axes of magnetization of the Dy3+ ions that lie in the plane of the triangle at 120 degrees one from each other. This gives rise to a peculiar chiral nature of the ground nonmagnetic doublet and to slow relaxation of the magnetization with abrupt accelerations at the crossings of the discrete energy levels.

Opening up a dysprosium triangle by ligand oximation

A simple trinuclear dysprosium complex shows complex slow relaxation of the magnetisation.

The Canted Antiferromagnetic Approach to Single Chain Magnets.

The reaction of manganese(III) acetate meso-tetraphenylporphyrin with phenylphosphinic acid provides the one-dimensional compound of formula [Mn(TPP)O2PHPh] x H2O, which crystallizes in the monoclinic C2/c space group. The chain structure is generated by a glide plane resulting in Jahn-Teller elongation axes of the MnIII octahedra that alternate along the chain. The phenylphosphinate anion transmits a sizable antiferromagnetic exchange interaction that, combined with the easy axis magnetic anisotropy of the MnIII sites, gives rise to a canted antiferromagnetic arrangement of the spins. The static single-crystal magnetic properties have been analyzed with a classical Monte Carlo approach, and the best fit parameters for the exchange and single ion anisotropy are J = -0.68(4) K and D = -4.7(2) K, respectively (using the -2JS(i)S(j) formalism for the exchange). Below 5 K the single-crystal dynamics susceptibility reveals a frequency-dependent out-of-phase signal typical of single-chain magnets. The extracted relaxation time follows the Arrhenius law with delta = 36.8 K. The dynamic behavior has been rationalized and correlated to geometrical parameters of the structure. The contribution of the correlation length to the energy barrier has been investigated, and it has been found that the characteristic length that dominates the dynamics strongly exceeds the correlation length estimated from magnetic susceptibility.

Long-range ferromagnetism of Mn12 acetate single-molecule magnets under a transverse magnetic field.

We use neutron diffraction to probe the magnetization components of a crystal of Mn12 single-molecule magnets. Each of these molecules behaves, at low temperatures, as a nanomagnet with spin S = 10 and strong anisotropy along the crystallographic c axis. The application of a magnetic field H(perpendicular) perpendicular to c induces quantum tunneling between opposite spin orientations, enabling the spins to attain thermal equilibrium. For T approximately < 0.9(1) K, this equilibrium state shows spontaneous magnetization, indicating the onset of ferromagnetism. These long-range magnetic correlations nearly disappear for mu0H(perpendicular) approximately > 5.5 T, possibly suggesting the existence of a quantum critical point.

Spin-density distribution in the new molecular magnet p-O2N·C6F4·CNSSN

Abstract Knowledge of the spin-density distribution in the dithiadiazolyl radical ring (DTDA) constitutes a major step towards the understanding of the magnetic and electronic properties of the rich magnetism of DTDA derivatives. The O 2 N·C 6 F 4 CNSSN radical was chosen as the most favourable CNSSN derivative to study the spin distribution in this kind of free radicals by polarised-neutron diffraction. Spin-density maps obtained for the O 2 N C 6 F 4 CNSSN radical show that almost all the spin density is localised on the sulphur and nitrogen atoms of the CNSSN ring. A small negative spin density on the carbon atom of the CNSSN ring and a negligible spin density over the rest of the radical are observed, in good agreement with ab initio calculations.

Prediction of the Equilibrium Structures and Photomagnetic Properties of the Prussian Blue Analogue RbMn(Fe(CN)6) by Density Functional Theory

A periodic density functional theory method using the B3LYP hybrid exchange-correlation potential is applied to the Prussian blue analogue RbMn[Fe(CN)6] to evaluate the suitability of the method for studying, and predicting, the photomagnetic behavior of Prussian blue analogues and related materials. The method allows correct description of the equilibrium structures of the different electronic configurations with regard to the cell parameters and bond distances. In agreement with the experimental data, the calculations have shown that the low-temperature phase (LT; Fe(2+)(t(6)2g, S = 0)-CN-Mn(3+)(t(3)2g e(1)g, S = 2)) is the stable phase at low temperature instead of the high-temperature phase (HT; Fe(3+)(t(5)2g, S = 1/2)-CN-Mn(2+)(t(3)2g e(2)g, S = 5/2)). Additionally, the method gives an estimation for the enthalpy difference (HT <--> LT) with a value of 143 J mol(-1) K(-1). The comparison of our calculations with experimental data from the literature and from our calorimetric and X-ray photoelectron spectroscopy measurements on the Rb0.97Mn[Fe(CN)6]0.98 x 1.03 H2O compound is analyzed, and in general, a satisfactory agreement is obtained. The method also predicts the metastable nature of the electronic configuration of the high-temperature phase, a necessary condition to photoinduce that phase at low temperatures. It gives a photoactivation energy of 2.36 eV, which is in agreement with photoinduced demagnetization produced by a green laser.

Antiferromagnetic single-chain magnet slow relaxation in the {Tb(α-fur)3}n polymer with non-Kramers ions

We report the synthesis, crystal structure and magnetic properties of a new molecular complex based on a Tb(III) ion supported by 2-furancarboxylic molecules: {Tb(α-fur)3(H2O)3}n (α-fur = C4H3OCOO). Two slightly different Tb sites (A and B) exist depending on the position of one of the dangling ligands. Ab initio calculations predict that, for both sites, the magnetic ground state is highly anisotropic (gz* = 17.8) and consists of a quasi-doublet with a small gap, well isolated from the next excited state. The α-fur ligand forms 1D polymeric chains of Tb ions of the same type (either A or B) running along the c-axis. The crystal structure is formed by the supramolecular stacking along the a-axis of 2D layers containing parallel chains of the same type. Static magnetization and heat capacity measurements show that, magnetically, the system can be modeled as an ensemble of Ising chains of non-Kramers Tb ions with effective spin S* = 1/2, antiferromagnetically (AF) coupled by a weak intrachain interaction (J*/kB = −0.135 K). At very low temperatures, the static susceptibility reflects the presence of a 2–4% concentration of defects in the chains. Ac susceptibility measurements at H = 0 performed down to mK temperatures have enabled us to observe the slow relaxation of magnetization through two different pathways. They are assigned to Single-Chain-Magnet (SCM) behavior in two different types of AF chains (A and B), triggered by the existence of defects breaking the chains into segments with short-range order. At temperatures below 0.1 K this mechanism is replaced by individual relaxation of the ions through direct processes. Under the application of a magnetic field the system slowly relaxes by two distinct direct processes, strongly affected by a phonon bottleneck effect.