Search Results (139)

Electronics evolution drives SMMs as a frontier, overcoming conventional magnetic material limits via molecular spin coupling. Two relevant Co(II) mononuclear complexes, [Co(MOP)₄(N₃)₂] (1) and [Co(MSP)₄(N₃)₂] (2) (MOP = 4-methoxypridine and MSP = 4-methylthiopyridine) were synthesized through changing the substituents of ligands. The Co(II) ions in the two complexes show octahedron coordination geometries. The replacement of the O to S in the equatorial plane leads to different Jahn–Teller effect because of the shorter Co(II)-N in the equatorial plane, resulting in the significantly different slow relaxation process confirmed by ab initio calculation. The results confirm the Co(II) ion is sensitive to ligand field. Full article

Ultrafast spin dynamics is a core research focus for advancing ultrafast spintronic devices, yet its accurate quantitative probing remains a challenge with conventional time-resolved techniques. Herein, we employ double-pump optical pump–terahertz emission spectroscopy (OPTE) to investigate the ultrafast spin dynamics of a Pt/Gd₁₉(Co_0.8Fe_0.2)₈₁/Ta ferrimagnetic rare-earth–transition-metal heterostructure. Experimental measurements resolve a single-step ultrafast demagnetization process with a characteristic time of ~0.42 ± 0.02 ps, followed by two-stage magnetic recovery involving a fast relaxation and a slow relaxation process. The fast and slow recovery time constants show a distinct positive dependence on the control pump fluence, increasing from 2.49 ± 0.11 ps to 3.28 ± 0.03 ps and 57.36 ± 11.28 ps to 164.96 ± 1.61 ps, respectively, as the pump fluence rises from 0.80 to 1.19 mJ/cm². The ~0.42 ps demagnetization timescale is consistent with that of 3d transition metals, indicating the transient magnetic response of the low-Gd-concentration heterostructure is dominated by the CoFe sublattice. Our findings validate that OPTE is an effective approach for the quantitative characterization of electron–lattice–spin coupling processes in spin-based heterostructures and provide critical experimental insights for controllable manipulation of ultrafast spin dynamics, laying a foundation for the design of ultrafast terahertz spintronic devices. Full article

The ligand-driven self-assembly of metal clusters offers a powerful strategy for constructing discrete molecular architectures with tunable magnetic and structural properties. By judiciously selecting appropriate multidentate ligands, researchers can direct the formation of polynuclear metal assemblies with diverse nuclearities, geometries, and topologies. Coordination-driven processes commonly stabilize such assemblies where multidentate ligands operate as templates and linkers. These will also determine how the metal centers are arranged in space and how they connect to each other. These clusters can take on shapes that range from basic bridging dimers to more complicated icosahedral and cubane-type motifs. They often have excellent symmetry and strong frameworks. Magnetically, these clusters are a great place to study exchange interactions, spin frustration, and the behavior of single-molecule magnets (SMMs). The magnetic characteristics depend on things like the type of metal ions, the bridging ligands, the overall shape, and the local coordination environment. Interestingly, a large number of ligand-assembled clusters exhibit high spin ground states and slow magnetization relaxation, which makes them attractive options for quantum information storage and molecular spintronic devices. This review connects coordination chemistry, supramolecular design, and molecular magnetism of pyridine–amine–carboxylate frameworks, offering insights into fundamental magnetic phenomena and guiding the development of next-generation functional materials. Continued exploration of ligand frameworks and metal combinations holds the potential to yield novel clusters with enhanced or unprecedented magnetic characteristics. Full article

A state-of-the-art tunnel magnetoresistance (TMR) sensor architecture, which is based on the perpendicularly magnetized magnetic tunnel junction (pMTJ), is introduced and engineered for ultrafast, high thermal stability, and linearity for magnetic field detection. Limitations in high-frequency environments, stemming from insufficient thermal stability and slow recovery times in conventional TMR sensors, are overcome by this approach. The standard MRAM structure is modified, and the Ruderman–Kittel–Kasuya–Yosida (RKKY) interaction is employed to give a strong, internal restoring torque to the storage layer magnetization. Sensor linearity is also ensured by this RKKY mechanism, and rapid relaxation to the initial spin state is observed when an external field is removed. The structural and magnetic properties of the multilayer stack are experimentally demonstrated. Robust synthetic antiferromagnetic (SAF) coupling is confirmed by using polar MOKE spectroscopy with an optimal Ru insertion layer thickness (0.6 nm), which is essential for high thermal stability. Subsequently, an ultrafast response of this TMR sensor architecture is probed by micromagnetic simulations. The storage layer magnetization rapidly recovers to the SAF state within an ultrashort time of 5.78 to 5.99 ns. This sub-6 ns recovery time scale suggests potential operation into the hundreds of MHz range. Full article

A centrosymmetric dinuclear complex, [Dy₂(H₂dapp)₂(μ-OH)₂(H₂O)₂]·4TCNQ·2CH₃OH, was synthesized using the TCNQ^·− radical anion (TCNQ = 7,7,8,8-tetracyanoquino-dimethane) and pentadentate nitrogen-containing Schiff base ligand (H₂dapp = 2,6-diacetylpyridine)-bis(2-pyridylhydrazone). In the Dy₂ dimer, the two Dy^III ions adopt eight-coordinated geometries intermediate between D_4d and D_2d symmetries, linked by two OH⁻ groups, with ferromagnetic Dy-Dy interactions. The TCNQ^·− radical anions are uncoordinated, and they pack tightly into antiparamagnetic dimers to balance the system charge. Under zero field, weak magnetic relaxation was observed, with an approximate Δ_eff = 2.82 K and τ₀ = 6.88 × 10⁻⁶ s. This might be attributed to the short intermolecular Dy···Dy distance of 7.97 Å, which could enhance intermolecular dipolar interactions and quantum tunneling of magnetization (QTM). Full article

Given the outstanding magnetic characteristics of lanthanide ions, the development of mononuclear or multinuclear lanthanide complexes becomes imperative. Previous research showed that a series of mononuclear Dy(III) complexes of rhodamine benzoyl hydrazone Schiff base ligands exhibit remarkable single-molecule magnetic properties and fluorescence. In this study, we used analogous ligands to synthesize lanthanide complexes [Dy(HL¹-o)(NO₃)₂(CH₃OH)₂]NO₃·CH₃OH (complex 1·MeOH) and tetranuclear complexes [Ln₄(L¹-c)₂(L²)₂(μ₃-OH)₂(NO₃)₂(CH₃OH)₄](NO₃)₂·2CH₃CN·5CH₃OH·2H₂O (Ln = Dy, complex 2; Ln = Gd, complex 3). Magnetic susceptibility measurements show that 1·2H₂O is a single-molecule magnet, 2 shows slow magnetic relaxation and 3 is a magnetic cooling material with the magnetic entropy change of 9.81 J kg⁻¹ K⁻¹ at 2 K and 5 T. The theoretical calculations on 1·MeOH indicate that it shows good magnetic anisotropy with the calculated energy barrier of 194.6 cm⁻¹. Full article

A dysprosium-based metal–organic framework (MOF), namely [DyLH₂O]_n (1) (H₃L = 4-((bis(carboxymethyl) amino)methyl)benzoic acid), was successfully synthesized via the hydrothermal method. According to the structural characterization, metal centers in this complex are linked by four bridges (two oxygens and two carboxylic groups), leading to Dy₂ units. On further connection by single carboxylic groups, the dimeric units extend to form a two-dimensional layer with a 4⁴ topological structure. Finally, the 2D layers were assembled into a 3D framework by the L⁻³ anions. A thermogravimetric test shows that [DyLH₂O]_n can maintain high thermal stability after losing water, until the temperature reaches 426 °C. Magnetic studies on 1 reveal antiferromagnetic exchange interactions of Dy³⁺…Dy³⁺ at low temperatures. Additionally, frequency-dependent out-of-phase signals were observed in alternating current (ac) magnetic susceptibility measurements for 1, indicating that it has slow magnetic relaxation features. Full article

We report the synthesis, structural characterization, and magnetic properties of three pentacoordinate Co(II) complexes [CoX(dppb)₂]X (X = Cl (1Cl), Br (2Br), and I (3I)) supported by the bidentate phosphine ligand 1,2-bis(diphenylphosphino)benzene (dppb). Single-crystal X-ray diffraction reveals that all three complexes adopt similar vacant octahedron (C_4v) geometries with the halide ligand in one axial position. Magnetic studies demonstrate that these complexes exhibit field-induced slow magnetic relaxation behaviors, with positive D values of 25.3(2), 21.6(1), and 19.4(2) cm⁻¹ for 1Cl, 2Br, and 3I, respectively. Detailed analysis of the relaxation dynamics reveals that Raman processes dominate at higher temperatures, with systematic variations in relaxation parameters across the series. The systematic variations in magnetic anisotropy and slow magnetic relaxation behaviors of the three complexes correlate with the decreasing electronegativity of the halide ligands. Full article

Organometallic rare-earth complexes have attracted considerable attention in recent years due to their unique structures and exceptional magnetic properties. In this study, we report the synthesis and magnetic characteristics of a family of monopentamethylcyclopentadienyl-coordinated trinuclear rare-earth hepta-chloride clusters [(Li(THF)(Et₂O))(Cp^*RE)₃(μ-Cl)₄(μ₃-Cl)₂(μ₄-Cl)] (RE₃: RE =Y, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu; Cp* = pentamethylcyclopentadienide). These clusters were synthesized by reacting LiCp* with RECl₃ in a 1:1 molar ratio within a mixed solvent system (THF: Et₂O = 1:9), resulting in high solubility in common organic solvents such as DCM, THF, and Et₂O. Magnetic studies conducted on these paramagnetic clusters reveal the coexistence of ferromagnetic and antiferromagnetic superexchange interactions in Gd₃. Additionally, Dy₃ exhibits both ferromagnetic and antiferromagnetic intramolecular dipolar interactions. Notably, slow magnetic relaxation was observed in Dy₃ below 23 K under a zero DC applied field with an energy barrier of 125(6) cm⁻¹. Full article

A ditopic ligand (H₂L₁), containing picolinate subunits segmented by ethynylene bridges, has been used in the synthesis of a series of isostructural coordination polymers, formulated as [(CH₃)₂NH₂][Ln(L₁)₂]·H₂O·CH₃COOH, where Ln = Eu (1), Gd (2), Tb (3), Dy (4) and Ho (5). The single-crystal structures show that these compounds crystallise in the orthorhombic Pna2₁ space group and form 3D anionic lattices with triangular cavities. AC magnetic susceptibility measurements show that the Gd, Tb and Dy derivatives (2–4) present a slow relaxation in their magnetisation under an applied DC magnetic field. The detailed study of the AC susceptibility in compounds 2 and 4 shows that they relax following direct and Orbach mechanisms under these conditions. The Dy derivative (4) retains this behaviour in the absence of an external field, relaxing via quantum tunnelling and Orbach mechanisms. Compound 2 is one of the very few reported Gd(III) compounds showing slow relaxation in its magnetisation. Full article

Herein, we present the synthesis and characterization of a series of isostructural lanthanide(III) compounds with the N-(4-carboxyphenyl)oxamic acid (H₃pcpa) ligand of the general formula as {[Ln₂(Hpcpa)₃(H₂O)₅]}_n [Ln = Dy(III) 1, Ho(III) 2, Er(III) 3]. The structure of 3 consists of neutral zig–zag chains of Er(III) ions, with Hpcpa^2– ligands acting as bridges in a bidentate/monodentate coordination mode with five water molecules achieving the eight-coordination around the two Er(III) ions within the repeating bis(carboxylate)-bridged dinuclear units along the chain. The magnetic and magnetocaloric properties were studied for 1–3. Compound 1 presents a field-induced slow relaxation of the magnetization with a “reciprocating thermal behavior” below 5 K for H = 0.25 T, while 2 shows maxima of the magnetic entropy from 3 up to 6 K for ΔH > 2 T. Full article

Four similar dinuclear lanthanide complexes have been synthesized by linking two [Ln(hfac)_2–3] units (hfac stands for hexafluoroacetylacetone) with different μ-O bridging ligands. The 2,2′-bipyridine-N-oxide ligand (bmpo) constructed two centrosymmetric complexes [Ln₂(hfac)₆(bmpo)₂] (Ln = Dy(1), Tb(2)), with nine-coordinated Ln^III ions showing C_s low symmetry, while the ligand di(2-pyridyl)methanediol (py₂C(OH)₂) formed another two compounds [Ln₂(hfac)₄(py₂C(OH)O)₂] (Ln = Dy(3), Tb(4)), with two kinds of eight-coordinated Ln^III ions exhibiting improved symmetries of D_4d and D_2d. Magnetic analysis reveals that Dy₂ complex 1 shows intramolecular antiferromagnetic coupling (J = −1.07 cm⁻¹) and no relaxation process above 2.0 K even in a 1000 Oe dc field, owing to the low symmetry of Dy^III ions, while the similar Dy₂ complex 3 with improved Dy^III symmetry shows ferromagnetic coupling (J = 1.17 cm⁻¹), which induces a 1000 Oe dc field-induced two-step magnetization relaxation processes with effective energy barrier U_eff = 47.4 K and 25.2 K for the slow relaxation and fast relaxation processes, respectively. This study proves again that the improved symmetry combined with intramolecular ferromagnetic interactions, both mediated by bridging ligands, can enhance the Dy^III anisotropy, further quench the quantum tunneling of the magnetization, and finally, enhance the magnetic behavior of Ln^III-based systems. Full article

Two mononuclear octahedral Co(II) complexes, [Co(L)X₂] (L = 1-(prop-2-en-1-yl)-1H-imidazole, X = NCS⁻ (1) and NCSe⁻ (2)), have been synthesized and characterized. The central Co(II) ions in two complexes adopt an octahedral geometry, coordinated by four N atoms from the ligand and two N atoms from the anion. Direct-current magnetic data revealed large easy-plane magnetic anisotropy in both 1 and 2. Dynamic magnetic measurements demonstrated that 1 and 2 display field-induced slow magnetic relaxation. For 1 and 2, the Raman mechanism is found to the dominant process in the whole temperature range. Compared to 1, the magnetic relaxation of 2 is faster, likely due to the presence of the hydrogen bonding system in 2. Full article

Herein, we present the synthesis and structural characterisation of two layered MOFs with the asymmetric ligand 3-chloro,6-cyano-2,5-dihydroxy-1,4-benzoquinone dianion (C₆O₄(CN)Cl²⁻ = chlorocyananilato). These compounds, formulated as (H₃O)[Eu(C₆O₄(CN)Cl)₂(H₂O)]·34H₂O (1) and (H₃O)[Dy(C₆O₄(CN)Cl)₂(H₂O)]·44H₂O (2), are isostructural and show a (4,4)-layered square structure with the crystallisation water molecules located between the layers. The lanthanoid ions are surrounded by four bis-bidentate chlorocyananilato ligands that connect each Ln^III centre with other four, giving rise to square cavities formed by Ln^III centres in the vertices and chlorocyananilato ligands as the sides. There is an additional coordinated water molecule that occupies the caped position of the capped square antiprismatic coordination geometry around the Ln^III centres. The magnetic properties show the presence of a field-induced slow relaxation of the magnetisation in the Dy^III derivative at low temperatures that follows Direct and Orbach relaxation mechanisms with an energy barrier of 36(3) K. Full article

Non-linear least squares (NLS) methods are commonly used for quantitative magnetic resonance imaging (MRI), especially for multi-exponential T1ρ mapping, which provides precise parameter estimation for different relaxation models in tissues, such as mono-exponential (ME), bi-exponential (BE), and stretched-exponential (SE) models. However, NLS may suffer from problems like sensitivity to initial guesses, slow convergence speed, and high computational cost. While deep learning (DL)-based T1ρ fitting methods offer faster alternatives, they often face challenges such as noise sensitivity and reliance on NLS-generated reference data for training. To address these limitations of both approaches, we propose the HDNLS, a hybrid model for fast multi-component parameter mapping, particularly targeted for T1ρ mapping in the knee joint. HDNLS combines voxel-wise DL, trained with synthetic data, with a few iterations of NLS to accelerate the fitting process, thus eliminating the need for reference MRI data for training. Due to the inverse-problem nature of the parameter mapping, certain parameters in a specific model may be more sensitive to noise, such as the short component in the BE model. To address this, the number of NLS iterations in HDNLS can act as a regularization, stabilizing the estimation to obtain meaningful solutions. Thus, in this work, we conducted a comprehensive analysis of the impact of NLS iterations on HDNLS performance and proposed four variants that balance estimation accuracy and computational speed. These variants are Ultrafast-NLS, Superfast-HDNLS, HDNLS, and Relaxed-HDNLS. These methods allow users to select a suitable configuration based on their specific speed and performance requirements. Among these, HDNLS emerges as the optimal trade-off between performance and fitting time. Extensive experiments on synthetic data demonstrate that HDNLS achieves comparable performance to NLS and regularized-NLS (RNLS) with a minimum of a 13-fold improvement in speed. HDNLS is just a little slower than DL-based methods; however, it significantly improves estimation quality, offering a solution for T1ρ fitting that is fast and reliable. Full article