Quantum Tunneling Relaxation Research Articles

Magnetic hysteresis and strong ferromagnetic coupling of sulfur-bridged Dy ions in clusterfullerene Dy2S@C82.

Two isomers of metallofullerene Dy2S@C82 with sulfur-bridged Dy ions exhibit broad magnetic hysteresis with sharp steps at sub-Kelvin temperature. Analysis of the level crossing events for different orientations of a magnetic field showed that even in powder samples, the hysteresis steps caused by quantum tunneling of magnetization can provide precise information on the strength of intramolecular Dy⋯Dy inter-actions. A comparison of different methods to determine the energy difference between ferromagnetic and antiferromagnetic states showed that sub-Kelvin hysteresis gives the most robust and reliable values. The ground state in Dy2S@C82 has ferromagnetic coupling of Dy magnetic moments, whereas the state with antiferromagnetic coupling in C s and C 3v cage isomers is 10.7 and 5.1 cm−1 higher, respectively. The value for the C s isomer is among the highest found in metallofullerenes and is considerably larger than that reported in non-fullerene dinuclear molecular magnets. Magnetization relaxation times measured in zero magnetic field at sub-Kelvin temperatures tend to level off near 900 and 3200 s in C s and C 3v isomers. These times correspond to the quantum tunneling relaxation mechanism, in which the whole magnetic moment of the Dy2S@C82 molecule flips at once as a single entity.

Near-infrared luminescence and solvent modulation of the magnetic relaxation behavior of dinuclear lanthanide complexess

Seven new dinuclear centrosymmetric complexes, [Ln2(dbm)2L2(DMF)2]·2DMF (Ln = Nd (1), Eu (2), Tb (3), Dy (4), Er (5), Yb (6)) and [Dy2(dbm)2L2(CH3OH)2]·2CH3OH (7) (Hdbm = 1,3-diphenyl-1,3-propanedione, H2L = 2-[(2-(amino)benzhydrazide)-methyl]-8-hydroxylquinoline, DMF = dimethyl-formamide) have been synthesized and structurally characterized. Dynamic magnetic studies reveal the slow magnetic relaxation of complexes 4 and 7 are influenced by a fast quantum tunneling relaxation of the magnetization (QTM). However, the different magnetic relaxation behaviors were observed apparently in the two Dy2 complexes under a 3000 Oe dc field and modulated by the subtle change of solvents from DMF to CH3OH. For complex 7, the temperature dependence curves of in-phase (χ′) and out-of-phase (χ″) show better frequency-dependent signals, suggesting a slow relaxation of magnetization, typical of SMM behavior. Fitting the dynamic magnetic data of complex 7 to the Arrhenius law gives the energy barrier Ueff/kB = 44.06 K with the pre-exponential factor τ0 = 2.17 × 10−7 s under a 3000 Oe dc field.

Slow Magnetic Relaxation in a Dysprosium Ammonia Metallocene Complex.

We report the serendipitous discovery and magnetic characterization of a dysprosium bis(ammonia) metallocene complex, [(C5Me5)2Dy(NH3)2](BPh4) (1), isolated in the course of performing a well-established synthesis of the unsolvated cationic complex [(C5Me5)2Dy][(μ-Ph)2BPh2]. While side reactivity studies suggest that this bis(ammonia) species owes its initial incidence to impurities in the DyCl3(H2O)x starting material, we were able to independently prepare 1 and its tetrahydrofuran (THF) derivative, [(C5Me5)2Dy(NH3)(THF)](BPh4) (2), from the reaction of [(C5Me5)2Dy][(μ-Ph)2BPh2] with ammonia in THF. The low-symmetry complex 1 exhibits slow magnetic relaxation under zero applied direct-current (dc) field to temperatures as high as 46 K and notably exhibits an effective barrier to magnetic relaxation that is more than 150% greater than that previously reported for the [(C5Me5)2Ln][(μ-Ph)2BPh2] precursor. On the basis of fitting of the temperature-dependent relaxation data, magnetic relaxation is found to occur via Orbach, Raman, and quantum-tunneling relaxation processes, and the latter process can be suppressed by the application of a 1400 Oe dc field. Field-cooled and zero-field-cooled dc magnetic susceptibility measurements reveal a divergence at 4 K indicative of magnetic blocking, and magnetic hysteresis was observed up to 5.2 K. These results illustrate the surprises and advantages that the lanthanides continue to offer for synthetic chemists and magnetochemists alike.

Axial Ligand Field in D4d Coordination Symmetry: Magnetic Relaxation of Dy SMMs Perturbed by Counteranions.

A series of mononuclear DyIII complexes with the general formula [DyLz2(salicylaldehyde)2]·X·solvent (Lz = 6-pyridin-2-yl[1,3,5]triazine-2,4-diamine; X = OH- (1·OH), Cl- (2·Cl), Br- (3·Br)) have been synthesized using mixed salicylaldehyde/pyridinyl-triazine ligands and discriminative counteranions. The DyIII ion in these three complexes resides in a similar D4d coordination geometry with counteranions perturbing the coordination environment and bond lengths and angles in the lattice. Magnetostructural studies reveal that the asymmetric distribution of salicylaldehyde/pyridinyl-triazine ligands and the presence of discriminative counteranions result in the coexistence of large anisotropy and quantum tunneling of magnetization. The magnetic anisotropy is dominated by the axial ligand field with short Dy-Osali distances and large ∠Osali-Dy-Osali angles, while the quantum tunneling relaxation is probably dictated by the π-π stacking of the Lz ligands, which induces an axial constriction of the coordinating plane. Ab initio calculations substantiate the diversity of the magnetic behaviors in these complexes and highlight the importance of axial ligand field with short Dy-Osali distances, large ∠Osali-Dy-Osali angles and less ligand stacking in these pseudo-D4d-symmetrical single-molecule magnets.

Unusual undecanuclear heterobimetallic Zn4Ln7 (Ln = Gd, Dy) nano-sized clusters encapsulating two peroxide anions through spontaneous intake of dioxygen.

The synthesis, characterization and properties of two unprecedented undecanuclear heterobimetallic Zn4Ln7 complexes of formula [Zn4Ln7(L)8(O2)2(OH)4(Cl)4(H2O)4]·Cl·4H2O·4CH3CN (Ln = Gd (1), Dy (2)) encapsulating two peroxide anions are presented, representing a very rare example of a 3d-peroxo-Ln system and expanding the realm of metal-peroxo complexes. These eleven metal ions are arranged in a peculiar structural motif, where Zn4 is located at the peripheral shell wrapping Ln7 in the inner core. The Zn ions are penta-coordinate in all cases, linked to the NO2 donor atoms from the L2- ligand and to a hydroxyl group, and the apical position is occupied by a chloride anion. All LnIII ions in these systems are octa-coordinate with LnO8 and LnNO7 coordination spheres. Magnetocaloric effect (MCE) behavior has been found in the Gd analogue due to multiple low lying excited states arising from antiferromagnetic Gd-Gd exchange interactions. The Dy derivative shows frequency dependent out-of-phase signals indicating the presence of slow relaxation of magnetization below 8 K under zero applied direct current (dc) field, but without reaching a maximum, which is due to a faster quantum tunneling relaxation. The effective barrier extracted from the frequency dependent data is Ueff = 11.2 K and a τ0 of 4.18 × 10-6 s.

Evaporable lanthanide single-ion magnet

Two thermally stable single-ion magnets containing a dysprosium ion with the ligand fod (1,1,1,2,2,3,3-heptafluoro-7,7-dimethyl-4,6-octadione) and bpy (2,2′-bipyridine) or phen (1,10-phenathroline) were synthesized, named 1Dy (Dyfod3bpy) and 2Dy (Dyfod3phen). They both have 6 oxygen atoms and 2 nitrogen atoms around the lanthanide metal ion in the center, forming a pseudo-D4d coordination structure. Dynamic magnetic studies show that they both exhibit temperature dependent processes and quantum tunneling relaxation under zero applied dc field. Interestingly, 1Dy melts at 90 °C and evaporates at 269 °C to form the amorphous compound 3Dy. The XRD data show that there is little change of the local structure between 1Dy and the evaporated sample 3Dy. Magnetic measurements show that 3Dy retains the SMM properties, but the relaxation barrier shifts from 87 K to 122 K and the quantum tunneling becomes slower.

Amending the anisotropy barrier and luminescence behavior of heterometallic trinuclear linear [M(II) -Ln(III) -M(II) ] (Ln(III) =Gd, Tb, Dy; M(II) =Mg/Zn) complexes by change from divalent paramagnetic to diamagnetic metal ions.

The sequential reaction of a multisite coordinating compartmental ligand [2-(2-hydroxy-3-(hydroxymethyl)-5-methylbenzylideneamino)-2-methylpropane-1,3-diol] (LH4 ) with appropriate lanthanide salts followed by the addition of [Mg(NO3 )2 ]⋅6 H2 O or [Zn(NO3 )2 ]⋅6 H2 O in a 4:1:2 stoichiometric ratio in the presence of triethylamine affords a series of isostructural heterometallic trinuclear complexes containing [Mg2 Ln](3+) (Ln=Dy, Gd, and Tb) and [Zn2 Ln](3+) (Ln=Dy, Gd, and Tb) cores. The formation of these complexes is demonstrated by X-ray crystallography as well as ESI-MS spectra. All complexes are isostructural possessing a linear trimetallic core with a central lanthanide ion. The comprehensive studies discussed involve the synthesis, structure, magnetism, and photophysical properties on this family of trinuclear [Mg2 Ln](3+) and [Zn2 Ln](3+) heterometallic complexes. [Mg2 Dy](3+) and [Zn2 Dy](3+) show slow relaxation of the magnetization below 12 K under zero applied direct current (dc) field, but without reaching a neat maximum, which is due to the overlapping with a faster quantum tunneling relaxation mediated through dipole-dipole and hyperfine interactions. Under a small applied dc field of 1000 Oe, the quantum tunneling is almost suppressed and temperature and frequency dependent peaks are observed, thus confirming the single-molecule magnet behavior of complexes [Mg2 Dy](3+) and [Zn2 Dy](3+) .

Zero-field quantum tunneling relaxation of the molecular spin in Fe8 observed by 57Fe Mössbauer spectrometry

57Fe Mössbauer spectrometry has been performed on oriented crystalline 57Fe enriched samples of Fe8 at 12 K under different applied magnetic fields. Fe8 has an S = 10 ground state and exhibits magnetic anisotropy with a barrier height of about 27 K. Under longitudinal magnetic fields, the energies of the spin levels coincide at steps of about 2.25 kOe, where tunneling relaxation occurs. We present here an experiment specially designed to observe quantum tunneling of molecular spin at zero field through Mössbauer. We report observation of quantum tunneling at temperatures of 12 K.

Two C3 -symmetric Dy3III complexes with triple di-μ-methoxo-μ-phenoxo bridges, magnetic ground state, and single-molecule magnetic behavior.

Two series of isostructural C(3)-symmetric Ln(3) complexes Ln(3)⋅[BPh(4)] and Ln(3)⋅0.33[Ln(NO(3))(6)] (in which Ln(III) =Gd and Dy) have been prepared from an amino-bis(phenol) ligand. X-ray studies reveal that Ln(III) ions are connected by one μ(2)-phenoxo and two μ(3)-methoxo bridges, thus leading to a hexagonal bipyramidal Ln(3)O(5) bridging core in which Ln(III) ions exhibit a biaugmented trigonal-prismatic geometry. Magnetic susceptibility studies and ab initio complete active space self-consistent field (CASSCF) calculations indicate that the magnetic coupling between the Dy(III) ions, which possess a high axial anisotropy in the ground state, is very weakly antiferromagnetic and mainly dipolar in nature. To reduce the electronic repulsion from the coordinating oxygen atom with the shortest Dy-O distance, the local magnetic moments are oriented almost perpendicular to the Dy(3) plane, thus leading to a paramagnetic ground state. CASSCF plus restricted active space state interaction (RASSI) calculations also show that the ground and first excited state of the Dy(III) ions are separated by approximately 150 and 177 cm(-1), for Dy(3)⋅[BPh(4)] and Dy(3)⋅0.33[Dy(NO(3))(6)], respectively. As expected for these large energy gaps, Dy(3)⋅[BPh(4)] and Dy(3)⋅0.33[Dy(NO(3)(6)] exhibit, under zero direct-current (dc) field, thermally activated slow relaxation of the magnetization, which overlap with a quantum tunneling relaxation process. Under an applied Hdc field of 1000 Oe, Dy(3)⋅[BPh(4)] exhibits two thermally activated processes with U(eff) values of 34.7 and 19.5 cm(-1), whereas Dy(3)⋅0.33[Dy(NO(3))(6)] shows only one activated process with Ueff =19.5 cm(-1).

Magnetic relaxation versus 3D long-range ordering in {Dy₂Ba(α-fur)₈}n furoate polymers.

A novel Dy-complex formulated as {[Dy2Ba(α-C4H3OCOO)8·(H2O)4]·2H2O}n, {Dy2Ba(α-fur)8}n, has been synthesized, structurally characterized, and magnetically and thermally investigated as a function of field and temperature, down to 85 mK. The α-furoate ligands consolidate 1D zig-zag chains formed by Dy2 dimers separated by Ba ions. Ab initio calculations were used to determine the easy anisotropy axis direction, the gyromagnetic tensor components and the energy levels of each Dy. The heat capacity and susceptibility measurements allowed us to conclude that intradimer and interdimer interactions are ferromagnetic and of the same order, J'/k(B) ≈ J''/k(B) = +0.55 K. In the absence of an applied magnetic field, the dynamic relaxation of the magnetization occurs through the fast (τ(T) ~ 10(-5) s) spin-reversal of each of the individual Dys through a quantum tunneling (QT) process. A long-range 3D ordered state is achieved at T(N) = 0.25 K, in which the ferromagnetically coupled zig-zag chains (J'/k(B) ≈ J''/k(B) = +0.528(1) K) running along the c-axis are antiferromagnetically coupled to the adjacent chains (J'''/k(B) = -0.021(1) K). Critical slowing down of the QT time constant is observed when the temperature approaches T(N). Under the application of a magnetic field, the QT relaxation is replaced by an Orbach process (with energy barrier U/k(B) = 68 K and τ0 ~ 10(-9) s at H = 2 kOe) and a very slow (τ(s) ∼ 0.2 s) relaxation process. We propose and demonstrate the proof of concept of a spintronic device, in which two different relaxation rates can be selected, and on/off switched by magnetic field biasing. The dynamical behavior of this compound is compared with another furoate to discuss the effect of competitive interactions.

Dilution-Triggered SMM Behavior under Zero Field in a Luminescent Zn2Dy2 Tetranuclear Complex Incorporating Carbonato-Bridging Ligands Derived from Atmospheric CO2 Fixation

The synthesis, structure, magnetic, and luminescence properties of the Zn2Dy2 tetranuclear complex of formula {(μ3-CO3)2[Zn(μ-L)Dy(NO3)]2}·4CH3OH (1), where H2L is the compartmental ligand N,N',N″-trimethyl-N,N″-bis(2-hydroxy-3-methoxy-5-methylbenzyl)diethylenetriamine, are reported. The carbonate anions that bridge two Zn(μ-L)Dy units come from the atmospheric CO2 fixation in a basic medium. Fast quantum tunneling relaxation of the magnetization (QTM) is very effective in this compound, so that single-molecule magnet (SMM) behavior is only observed in the presence of an applied dc field of 1000 Oe, which is able to partly suppress the QTM relaxation process. At variance, a 1:10 Dy:Y magnetic diluted sample, namely, 1', exhibits SMM behavior at zero applied direct-current (dc) field with about 3 times higher thermal energy barrier than that in 1 (U(eff) = 68 K), thus demonstrating the important role of intermolecular dipolar interactions in favoring the fast QTM relaxation process. When a dc field of 1000 Oe is applied to 1', the QTM is almost fully suppressed, the reversal of the magnetization slightly slows, and U(eff) increases to 78 K. The dilution results combined with micro-SQUID magnetization measurements clearly indicate that the SMM behavior comes from single-ion relaxation of the Dy(3+) ions. Analysis of the relaxation data points out that a Raman relaxation process could significantly affect the Orbach relaxation process, reducing the thermal energy barrier U(eff) for slow relaxation of the magnetization.

Octanuclear {Ln(III)8}(Ln = Gd, Tb, Dy, Ho) Macrocyclic Complexes in a Cyclooctadiene-like Conformation: Manifestation of Slow Relaxation of Magnetization in the Dy(III) Derivative

The synthesis of a series of macrocyclic, isostructural octanuclear lanthanide complexes [Gd8 (LH2)4 (μ-Piv)4 (η(2)-Piv)4 (μ-OMe)4]·6CH3OH·2H2O (1), [Tb8 (LH2)4 (μ-Piv)4 (η(2)-Piv)4 (μ-OMe)4]4CH3OH·4H2O (2), [Dy8(LH2)4 (μ-Piv)4 (η(2)-Piv)4 (μ-OMe)4]·8CH3OH (3), and [Ho8(LH2)4(μ-Piv)4 (η(2)-Piv)4 (μ-OMe)4]·CH3OH·4H2O (4) have been achieved, using Ln(III) nitrate salts, pivalic acid, and a new multidentate chelating ligand (2E,N'E)-N'-(3-((bis(2- hydroxyethyl)amino)methyl)-2-hydroxy-5-methylbenzylidene)-2-(hydroxyimino) propane hydrazide (LH5), containing two unsymmetrically disposed arms; one side of the phenol unit is decorated with a diethanolamine group while the other side is a hydrazone that has been built by the condensation reaction involving 2-hydroxyiminopropanehydrazide. All the compounds, 1-4, are neutral and are held by the four [LH2](3-) triply deprotonated chelating ligands. In these complexes all the lanthanide ions are doubly or triply bridged via phenolate, alkoxy, and pivalate oxygens. The metal centers are distributed over the 8 vertices of an octagon, resembling a cyclooctadiene ring core. The details of magnetochemical analysis for complexes 1-4 shows that they exhibit antiferromagnetic interactions between the Ln(3+) ions through the phenoxo, alkoxo, and pivalato bridging groups. None of the compounds exhibits slow relaxation of the magnetization at zero applied direct current (dc) magnetic field, which could be due to the existence of a fast quantum tunneling relaxation of the magnetization (QTM). In the case of 3, the application of a small dc field is enough as to fully or partly suppress the fast and efficient zero-field QTM allowing the observation of slow relaxation above 2 K.

Two Locally Chiral Dysprosium Compounds with Salen‐Type Ligands That Show Slow Magnetic Relaxation Behavior

AbstractTwo Dy compounds, [Dy4(μ4‐O)L2(C6H5COO)6]·3CH3OH (1) and [Dy2L(H2L)(teaH2)(o‐vanillin)(H2O)](ClO4)2·2CH3OH·H2O (2, teaH3 = triethanolamine), were assembled by the reactions of the salen‐type ligand N,N′‐bis(3‐methoxysalicylidene)‐1,2‐cyclohexanediamine (H2L) and different dysprosium salts and bases. These compounds show both local chirality and slow magnetic relaxation. The former is induced by an unprecedented coordination mode of the ligand H2L, in which the N2O2 pocket encapsulates one Dy ion. Compound 1, which has four Dy ions in distinct coordination environments, demonstrates the rare Dy4 tetrahedron motif supported by a central μ4‐O atom, which is akin to a chiral carbon atom in organic molecules, as revealed by single‐crystal X‐ray analyses. In contrast, the formation of 2, which shows an unusual structural motif with a tail, is driven by the presence of triethanolamine. In spite of the low‐symmetry coordination geometry around each Dy ion, both compounds display slow magnetic relaxation behavior, but with fast quantum tunneling relaxation, as indicated by alternating current (ac) susceptibility measurements.

Magnetic nanoparticles

Intrinsic properties of magnetic nanoparticles are reviewed, with special emphasis on the effects of finite size on zero-temperature spin ordering, magnetic excitations, and relaxation. Effects on zero-temperature spin ordering include moment enhancement due to band narrowing in 3d transition metal particles, surface spin disorder in ferrite particles, and multi-sublattice states in antiferromagnetic oxide particles. Magnetic excitations include discretized spin wave modes, and surface modes that have been detected by quasielastic neutron scattering. Thermally activated and quantum tunneling relaxation is discussed in the context of ideal single-domain particles, as well as particles with surface spin disorder.

Quantum relaxation in the low-temperature magnetic susceptibility of the amorphous alloya−Tb2Fe

The ac magnetic susceptibility of melt spun ribbons of the strong-random magnetic-anisotropy amorphous alloy $a\ensuremath{-}{\mathrm{Tb}}_{2}\mathrm{Fe}$ has been measured from room temperature down to 0.10 K. In the temperature region $4<T<300\mathrm{K}$ the system behaves as a random anisotropy sperimagnet, with freezing temperature ${T}_{f}=160\mathrm{K}.$ In-phase ${\ensuremath{\chi}}^{\ensuremath{'}}$ and out-of-phase ${\ensuremath{\chi}}^{\ensuremath{''}}$ components of the susceptibility deviate from the classical linear temperature dependence to a temperature-independent value below a crossover temperature ${T}_{Q}\ensuremath{\approx}3\mathrm{K}.$ The low-temperature ``plateau'' behavior supports the existence of magnetic quantum tunneling relaxation. The tunneling entities are spin drops which comprise an average number $n\ensuremath{\approx}11$ spins.