Recent Developments in Lanthanide Single‐Molecule Magnets

Single‐molecule magnets (SMMs) exhibiting slow relaxation of magnetization of purely molecular origin are highly attractive owing to their potential applications in spintronic devices, high‐density information storage, and quantum computing. In particular, lanthanide SMMs have been playing a major role in the advancement of this field because of the large intrinsic magnetic anisotropy of lanthanide metal ions. Herein, some recent breakthroughs that are changing the perspective of the field are highlighted, with special emphasis on synthetic strategies towards the design of high‐performance SMMs.     

Passive effects of rare-earth permanent magnets on flexible conductive structures

The paper presents a theoretical and experimental study of vibrating structures where paramagnetic or diamagnetic systems interact with rare-earth passive magnets.The theoretical model of the system is focused on the damping properties of permanent magnets and on their interactions with the dynamic behaviour of an Euler–Bernoulli beam. In particular, the magnetic model is based on the analogy of the equivalent currents method in a quasi-static open-circuit-type configuration and it is used to determine the influence of eddy currents on the dynamic behaviour of conducting material structures. The magnetic effects are characterised by a viscous-type damping and by a stiffening dynamic effect of the structure, called “phantom effect”.The authors present the experimental outcomes for uniform cantilever clamped-free beams of different kinds of paramagnetic or diamagnetic conducting materials. It appears that the system frequency response can be modified by the presence of a pair of concordant or discordant permanent magnets of high residual induction settled at the free end.Through the comparison between theoretical and experimental results, the paper demonstrates the validity of the model, that is able to describe both the above mentioned effect of dynamic stiffening of the structure and the considerable localised damping properties in paramagnetic or diamagnetic materials having low electric resistivity.     

Spectroscopic and magnetic investigations of actinide‐based nanomagnets

Magnetic exchange is an essential feature of transition‐metal nanomagnets because it combines the relatively low spin‐only moments of several ions into a “giant spin” ground state, which can make slow magnetic relaxation very favorable in an axially anisotropic environment. In contrast, most of the early research on lanthanide‐based complexes focused on single‐ion magnets, where the required large moment is generated by the unquenched orbital contribution (which is parallel to the spin in heavy rare earths). With their unfilled 5f electronic shell being on the verge between localization and itinerancy, actinides are expected to combine the best of both 3d and 4f metals in terms of exchange and anisotropy, and are therefore under consideration as potential building blocks for the next generation of single‐molecule magnets. In this Perspective, a review of the recent development in this field is given, and some discrepancies between the spectroscopic and magnetic data are discussed. © 2014 European Commission. International Journal of Quantum Chemistry published by Wiley Periodicals, Inc.     

Cyanide-bridged [Fe8M6] clusters displaying single-molecule magnetism (M=Ni) and electron-transfer-coupled spin transitions (M=Co)

Cyanide‐bridged metal complexes of [Fe₈M₆(μ‐CN)₁₄(CN)₁₀ (tp)₈(HL)₁₀(CH₃CN)₂][PF₆]₄?n CH₃CN?m H₂O (HL=3‐(2‐pyridyl)‐5‐[4‐(diphenylamino)phenyl]‐1H‐pyrazole), tp^?=hydrotris(pyrazolylborate), 1 : M=Ni with n=11 and m=7, and 2 : M=Co with n=14 and m=5) were prepared. Complexes 1 and 2 are isomorphous, and crystallized in the monoclinic space group P2₁/n. They have tetradecanuclear cores composed of eight low‐spin (LS) Fe^III and six high‐spin (HS) M^II ions (M=Ni and Co), all of which are bridged by cyanide ions, to form a crown‐like core structure. Magnetic susceptibility measurements revealed that intramolecular ferro‐ and antiferromagnetic interactions are operative in 1 and in a fresh sample of 2 , respectively. Ac magnetic susceptibility measurements of 1 showed frequency‐dependent in‐ and out‐of‐phase signals, characteristic of single‐molecule magnetism (SMM), while desolvated samples of 2 showed thermal‐ and photoinduced intramolecular electron‐transfer‐coupled spin transition (ETCST) between the [(LS‐Fe^II)₃(LS‐Fe^III)₅(HS‐Co^II)₃(LS‐Co^III)₃] and the [(LS‐Fe^III)₈(HS‐Co^II)₆] states.     

Capping ligand perturbed slow magnetic relaxation in dysprosium single-ion magnets

Single-ion magnets 1 and 2 and their diamagnetic analogues 3 and 4 for magnetic-site dilution were obtained through substitution of the coordinated water molecules of [Ln(TTA)(3)(H(2)O)(2)] (Ln=Dy (1, 2), Y (3, 4); TTA=4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedionate) by 2,2'-bipyridine (1, 3) and 1,10-phenanthroline (2, 4) capping ligands. Their structures and magnetic properties were investigated with the goal of identifying features relevant to modulating relaxation dynamics of single-ion magnets. The metal ions in all complexes adopt an approximately square-antiprismatic (SAP) O(6)N(2) coordination environment. The SAP polyhedrons for both 1 and 2 show slight longitudinal compression, while the coordination sphere of 1 deviates more from an ideal SAP than that of 2, as indicated by the skew angles of the SAP environment. The similar values of U(eff) for the two magnetically diluted samples imply nearly the same distribution of low-lying states for their Dy(III) centers, which is consistent with the slight axial contraction observed for 1 and 2 and further corroborated by ligand-field analysis. The fast quantum tunneling rate τ(QTM) of 1, which is about ten times faster than that of 2, can presumably be associated with the larger rotation of the SAP surroundings. This distortion may result in a significant transverse anisotropy terms, and thus strongly affect the dynamic behavior of the system.     

脉管制冷用于低温超导磁体冷却的可行性分析

采用制冷机直接冷却的低温超导磁体系统与传统液氮冷却方式相比，具有轻便紧凑、运行简单、维护方便、可长时间连续运行等优点；而脉管制冷由于冷端无运动部件，与传统的G-M制冷机相比，具有结构简单、运行可靠、振动小等优点．本文结合我们在液氮温区脉管制冷方面的技术，从漏热和经济性两方面探讨了将脉管制冷直接用于冷却一个5特斯拉NbTi低温超导磁体的可行性，为后期系统的搭建奠定基础．     

High coercivity nanocrystalline YCo5 powders produced by mechanical milling

High coercivity nanostructured YCo₅ powders were successfully prepared by mechanical milling of as-cast alloys and subsequent vacuum annealing. Almost single phase YCo₅ alloys, obtained by arc melting, were processed by high energy mechanical milling using a SPEX 8000 mill. After 4 h of milling, powders become nearly amorphous. DSC scans revealed the existence of an irreversible broad exothermic transition with a maximum at 516 °C associated with the crystallization process. Annealing in high vacuum at 800 °C during 2.5 min led to the formation of YCo₅ nanoparticles with an average particle size of 12 nm. A high intrinsic coercivity of 7.23 kOe together with a σ_r/σ_s ratio of 0.75 were obtained.