Spin-Phonon Coupling and Slow-Magnetic Relaxation in Pristine Ferrocenium.

We report the spin dynamic properties of non-substituted ferrocenium complexes. Ferrocenium shows a field-induced single-molecule magnet behaviour in DMF solution while cobaltocene lacks slow spin relaxation neither in powder nor in solution. Multireference quantum mechanical calculations give a non-Aufbau orbital occupation for ferrocenium with small first excitation energy that agrees with the relatively large measured magnetic anisotropy for a transition metal S=1/2 system. The analysis of the spin relaxation shows an important participation of quantum tunnelling, Raman, direct and local-mode mechanisms which depend on temperature and the external field conditions. The calculation of spin-phonon coupling constants for the vibrational modes shows that the first vibrational mode, despite having a low spin-phonon constant, is the most efficient process for the spin relaxation at low temperatures. In such conditions, vibrational modes with higher spin-phonon coupling constants are not populated. Additionally, the vibrational energy of this first mode is in excellent agreement with the experimental fitted value obtained from the local-mode mechanism.

Magnetic anisotropy in YbIII complex candidates for molecular qubits: a theoretical analysis.

The magnetic properties of mononuclear YbIII complexes have been explored by using multiconfigurational CASPT2/RASSI calculations. Such complexes, in particular the case of [Yb(trensal)] complex, have been proposed as molecular qubits due to their spin dynamics properties. We have verified the accuracy of the theoretical approach to study such systems by comparing with experimental magnetic data. In order to have a wide overview of the magnetic properties of mononuclear YbIII complexes, we have considered simple charged and neutral models, [Yb(H2O)n]3+ and [Yb(OH)3(H2O)n-3], for many coordination modes. Thus, the results for more than 100 models allow extraction of some conclusions about the best ligand distributions in the coordination sphere to tailor the magnetic properties. Some low coordination, between 3 and 5, complexes that have no experimental magnetic data have been studied computationally to check if they can present high magnetic anisotropy.

Magnetization Slow Dynamics in Ferrocenium Complexes.

The single-molecule magnet (SMM) properties of a series of ferrocenium complexes, [Fe(η5 -C5 R5 )2 ]+ (R=Me, Bn), are reported. In the presence of an applied dc field, the slow dynamics of the magnetization in [Fe(η5 -C5 Me5 )2 ]BArF are revealed. Multireference quantum mechanical calculations show a large energy difference between the ground and first excited states, excluding the commonly invoked, thermally activated (Orbach-like) mechanism of relaxation. In contrast, a detailed analysis of the relaxation time highlights that both direct and Raman processes are responsible for the SMM properties. Similarly, the bulky ferrocenium complexes, [Fe(η5 -C5 Bn5 )2 ]BF4 and [Fe(η5 -C5 Bn5 )2 ]PF6 , also exhibit magnetization slow dynamics, however an additional relaxation process is clearly detected for these analogous systems.

[UF6 ]2- : A Molecular Hexafluorido Actinide(IV) Complex with Compensating Spin and Orbital Magnetic Moments.

The first structurally characterized hexafluorido complex of a tetravalent actinide ion, the [UF6 ]2- anion, is reported in the (NEt4 )2 [UF6 ]⋅2 H2 O salt (1). The weak magnetic response of 1 results from both UIV spin and orbital contributions, as established by combining X-ray magnetic circular dichroism (XMCD) spectroscopy and bulk magnetization measurements. The spin and orbital moments are virtually identical in magnitude, but opposite in sign, resulting in an almost perfect cancellation, which is corroborated by ab initio calculations. This work constitutes the first experimental demonstration of a seemingly non-magnetic molecular actinide complex carrying sizable spin and orbital magnetic moments.

Mononuclear Lanthanide Complexes with 18-Crown-6 Ether: Synthesis, Characterization, Magnetic Properties, and Theoretical Studies.

A family of lanthanide metal complexes with the general formula [Ln(H2O)3(18-crown-6)](ClO4)3 (Ln = TbIII, DyIII, ErIII, and YbIII) has been synthesized. Their magnetic properties have been characterized by direct- and alternating-current SQUID measurements and analyzed with the help of CASSCF-type calculations. The DyIII and YbIII compounds show slow relaxation of magnetization under an external magnetic field. Analysis of the dependence of the relaxation time with the temperature and external magnetic field reveals that the main contributions are the quantum tunneling and Raman relaxation terms, respectively. Analysis of the ß electron density and electrostatic potentials indicates that the axial ligands (three water molecules) generate a relatively small repulsion, with the lanthanide electron density being the reason for the moderate magnetic anisotropy found in these systems.

Predetermined Ferromagnetic Coupling via Strict Control of M-O-M Angles.

An imidazolidine-phenolate ligand HL yields quadruple-bridged (µ-NCNimidazolidine)2(µ-Ophenolate)2 ferromagnetic dinuclear nickel and cobalt complexes. Both kinds of bridges contribute to the ferromagnetic coupling, but the ferromagnetism of these samples is mainly ascribed to the double µ-Ophenolate links, on the basis of density functional theory calculations. These studies demonstrate not only that the short M-O-M angles of the M2O2 cores favors the parallel alignment of the electrons but also that these angles are the optimal ones for maximizing the ferromagnetic contribution in these complexes. And these acute angles, close to 90°, are predetermined by the geometrical constrictions imposed by the ligand itself. Thus, HL is an uncommon polydentate donor that induces ferromagnetism per se in its metal complexes by strict control of one geometric parameter, the M-O-M angle.

Slow-spin relaxation of a low-spin S = 1/2 FeIII carborane complex.

In this communication, we report the first evidence of slow-spin relaxation of a low-spin FeIII carborane complex. Iron S = 1/2 complexes showing such behaviour are particularly appealing as qubit candidates because they fulfil some of the main requirements to reach long decoherence times, such as moderate magnetic anisotropy, small spin, metal element mainly with zero-nuclear spin and furthermore, large versatility to introduce chemical modifications.

A Low Spin Manganese(IV) Nitride Single Molecule Magnet.

Structural, spectroscopic and magnetic methods have been used to characterize the tris(carbene)borate compound PhB(MesIm)3Mn≡N as a four-coordinate manganese(IV) complex with a low spin (S = 1/2) configuration. The slow relaxation of the magnetization in this complex, i.e. its single-molecule magnet (SMM) properties, is revealed under an applied dc field. Multireference quantum mechanical calculations indicate that this SMM behavior originates from an anisotropic ground doublet stabilized by spin-orbit coupling. Consistent theoretical and experiment data show that the resulting magnetization dynamics in this system is dominated by ground state quantum tunneling, while its temperature dependence is influenced by Raman relaxation.