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We report here a linear fluoride-bridged Double-Decker Dysprosium metallacrown with high-performance SMM. The successful introduction of stronger magnetic exchange-coupling in the axial direction, which is collinear with the Ising-type magnetic anisotropy axis of dysprosium ions, plays a pivotal role in improving the SMM properties of the double-decker Dysprosium metallacrown.

Single-molecule magnets (SMMs) exhibiting open hysteresis loops may potentially apply to molecule-based information processing and storage. However, the capacity to retain magnetic memory is always limited by zero-field quantum tunneling of magnetization (QTM). Herein, a well-designed dysprosium metallacrown SMM, consisting of an endohedral approximate linear F-Dy-F strong anisotropic moiety in a peripheral [15-MCNi-5] metallacrown (MC), is reported with the largest reversal barrier of 1060 cm-1 among d-f SMMs. Rectangle-like hysteresis loops are observed with the huge squareness (remanence/saturation magnetization) up to 97% at 2 K. More importantly, zero-field QTM step is phenomenologically removed by minimizing the dipole coupling and hyperfine interactions. The results demonstrate for the first time that zero-field QTM step can be eliminated via manipulating the ligand field and vanishing the external magnetic perturbations, which illuminates a promising blueprint for developing high-performance SMMs.

Single-molecule magnets (SMMs) are promising elements for quantum informatics. In the presence of strong magnetic anisotropy, they exhibit magnetization blocking - a magnetic memory effect at the level of a single molecule. Recent studies have shown that the SMM performance scales with the height of magnetization blocking barrier. By employing molecular engineering this can be significantly modified, remaining independent from other external factors such as magnetic field. Taking advantage of hyperfine coupling of electronic and nuclear spins further enhances their functionality, however, a poor understanding of relaxation mechanisms in such SMMs limits the exploitation of nuclear-spin molecular qubits. Here we report the opening discovery of field-dependent oscillation of the magnetization blocking barrier in a new holmium metallacrown magnet driven by the switch of relaxation mechanisms involving hyperfine interaction. Single-crystal magnetic hysteresis measurements combined with first-principles calculations reveal an activated temperature dependence of magnetic relaxation dominated either by incoherent quantum tunneling of magnetization at anti-crossing points of exchange-hyperfine states or by Orbach-like processes at crossing points. We demonstrate that these relaxation mechanisms can be consecutively switched on and off by increasing the external field, which paves a way for manipulating the magnetization dynamics of SMMs using hyperfine interaction., Comment: 6 pages, 4 figures

In 2016, we reported a single-ion magnet [Dy(bbpen)Br] with an energy barrier over 1000 K. Here a dimeric [Dy2(mu-CO3)(bbpen)2(H2O)].H2O.CH3OH (1) and a trimeric [Dy3(mu3-CO3)(bppen)3](CF3SO3).H2O (2) single-molecule magnets (SMMs) were obtained through replacing the Br- anion with the carbonate bridge. Their effective relaxation barriers at zero dc field are decrease to 51 K and 422 K, respectively, which are consist with their structural modifications.

The interplay of strong single-ion anisotropy and magnetic interactions often give rise to novel magnetic behavior and can provide additional routes for controlling magnetization dynamics. However, novel effects arising from interactions between lanthanide and transition-metal ions are nowadays rarely observed. Herein, a {$Dy^{III}Cu^{II}_5$} 3d-4f single-molecule magnet (SMM) is constructed as a rigid and planar [15-MC-5] metallacrown (MC), where the $Dy^{III}$ ion is trapped in the central pseudo-$D_{5h}$ pocket. A strong axial crystal field (CF) imbues the $Dy^{III}$ ion with large Ising-type magnetic anisotropy, and we are able to observe and model the magnetic interactions between the $Cu^{II}-Cu^{II}$ and $Dy^{III}-Cu^{II}$ pairs. Butterfly-shaped magnetic hysteresis shows clear steps at $\pm$0.4 T, coincident with level crossings in our model exchange Hamiltonian between the {$Cu^{II}_5$} and $Dy^{III}$ spin systems. Most intriguingly, this air-stable SMM exhibits three distinct regimes in its magnetic relaxation dynamics, all clearly displaying an exponential dependence on temperature.

The magnetic susceptibility and isothermal magnetization for GdF3 were measured, and the isothermal entropy change was evaluated up to 9 T. Combining the large isotropic spin of Gd3+, the dense structure and the weak ferromagnetic interaction, an extremely large -(delta)Sm for GdF3 was observed up to 528 mJ cm-3 K-1 for (delta)H = 9 T, proving itself to be the best cryogenic magnetic coolant ever., Comment: 4 Pages, 5 Figures, 1 Table

The excellent magnetocaloric effect of a dense inorganic framework, orthorhombic Gd(OH)CO3, is evaluated by isothermal magnetization and heat capacity measurements. The large -{\Delta}Sm, both in gravimetric and volumetric units, place it as a great candidate for cryogenic magnetic cooler., Comment: 6 Pages, 10 Figures, 2 Tables