Grafting Single Molecule Magnets on Gold Nanoparticles

The chemical synthesis and characterization of the first hybrid material composed by gold nanoparticles and single molecule magnets (SMMs) are described. Gold nanoparticles are functionalized via ligand exchange using a tetrairon(III) SMM containing two 1,2‐dithiolane end groups. The grafting is evidenced by the shift of the plasmon resonance peak recorded with a UV–vis spectrometer, by the suppression of nuclear magnetic resonance signals, by X‐ray photoemission spectroscopy peaks, and by transmission electron microscopy images. The latter evidence the formation of aggregates of nanoparticles as a consequence of the cross‐linking ability of Fe₄ through the two 1,2‐dithiolane rings located on opposite sides of the metal core. The presence of intact Fe₄ molecules is directly proven by synchrotron‐based X‐ray absorption spectroscopy and X‐ray magnetic circular dichroism spectroscopy, while a detailed magnetic characterization, obtained using electron paramagnetic resonance and alternating‐current susceptibility, confirms the persistence of SMM behavior in this new hybrid nanostructure.     

Synthesis and Magnetic Properties of Mn<Subscript>12</Subscript>-Based Single Molecular Magnets with Benzene and Pentafluorobenzene Carboxylate Ligands

We report on the synthesis and magnetic properties of Mn₁₂-based single molecular magnets (SMMs) with benzene and pentafluorobenzene carboxylate ligands. The changes in ligand structure are shown to have a decisive effect on the magnetic properties of the complexes produced. The compound with benzene demonstrates an unusual magnetic behavior, namely, temperature dependencies of magnetization taken under the zero-field-cooled and field-cooled conditions are split below 10 K and furthermore remnant magnetization and coercive force remain nonzero in this temperature range. In contrast, the compound with pentafluorobenzene displays the customary signatures of the blocking temperature at 3 K. The effect of ligand substitution was theoretically studied within the local density approximation taking into account on-site Coloumb repulsion. Calculation results confirm that the electronic structure and the magnetic exchange interactions between different Mn atoms strongly depend on the type of ligand.     

Chiromagnetic Plasmonic Nanoassemblies with Magnetic Field Modulated Chiral Activity

Chiral plasmonic nanoassemblies, which exhibit outstanding chiroptical activity in the visible or near‐infrared region, are popular candidates in molecular sensing, polarized nanophotonics, and biomedical applications. Their optical chirality can be modulated by manipulating chemical molecule stimuli or replacing the building blocks. However, instead of irreversible chemical or material changes, real‐time control of optical activity is desired for reversible and noninvasive physical regulating methods, which is a challenging research field. Here, the directionally and reversibly switching optical chirality of magneto‐plasmonic nanoassemblies is demonstrated by the application of an external magnetic field. The gold‐magnetic nanoparticles core–satellite (Au@Fe₃O₄) nanostructures exhibit chiral activity in the UV–visible range, and the circular dichroism signal is 12 times greater under the magnetic field. Significantly, the chiral signal can be reversed by regulating the direction of the applied magnetic field. The attained magnetic field‐regulated chirality is attributed to the large contributions of the magnetic dipole moments to polarization rotation. This magnetic field‐modulated optical activity may be pivotal for photonic devices, information communication, as well as chiral metamaterials.     

Inside Front Cover: Self‐Assembly and Magnetism of Mn12 Nanomagnets on Native and Functionalized Gold Surfaces (Adv. Mater. 13/2005)

Single molecule magnets (SMMs) are likely to find applications as elementary units in data storage and spin electronics. The deterministic organization of SMMs on a surface is a prerequisite for their individual addressing with a scanning probe tip. On p. 1612, Bucher and co‐workers present a molecular‐scale STM study of the successive self‐assembling steps of Mn₁₂L on a Au(111) surface, as illustrated on the inside cover. The molecules in the monolayer keep their magnetism, as observed by SQUID magnetometry, although the broadening of quantum effects compared to the bulk material refers to a distribution of molecular environment.     

Intrinsic Van Der Waals Magnetic Materials from Bulk to the 2D Limit: New Frontiers of Spintronics

2D van der Waals (vdW) magnets, which present intrinsic ferromagnetic/antiferromagnetic ground states at finite temperatures down to atomic‐layer thicknesses, open a new horizon in materials science and enable the potential development of new spin‐related applications. The layered structure of vdW magnets facilitates their atomic‐layer cleavability and magnetic anisotropy, which counteracts spin fluctuations, thereby providing an ideal platform for theoretically and experimentally exploring magnetic phase transitions in the 2D limit. With reduced dimensions, the susceptibility of 2D magnets to a large variety of external stimuli also makes them more promising than their bulk counterpart in various device applications. Here, the current status of characterization and tuning of the magnetic properties of 2D vdW magnets, particularly the atomic‐layer thickness, is presented. Various state‐of‐the‐art optical and electrical techniques have been applied to reveal the magnetic states of 2D vdW magnets. Other emerging 2D vdW magnets and future perspectives on the stacking strategy are also given; it is believed that they will excite more intensive research and provide unprecedented opportunities in the field of spintronics.     

Cover Picture: Nanoscale Deposition of Single‐Molecule Magnets onto SiO2 Patterns (Adv. Mater. 2/2007)

The cover shows a schematic of scanning probe nanolithography based on the spatial confinement of an oxidation reaction within a water meniscus, and its application for fabricating ordered arrays of cationic Mn12 single‐molecule magnets. Romero, Coronado, Garcìa, and co‐workers report on p. 291 that electrostatic interactions between the molecules and trapped charges within the nanodots drive the positioning of the molecules at the nanoscale.     

Anatomy of Skyrmionic Textures in Magnetic Multilayers

Room temperature magnetic skyrmions in magnetic multilayers are considered as information carriers for future spintronic applications. Currently, a detailed understanding of the skyrmion stabilization mechanisms is still lacking in these systems. To gain more insight, it is first and foremost essential to determine the full real‐space spin configuration. Here, two advanced X‐ray techniques are applied, based on magnetic circular dichroism, to investigate the spin textures of skyrmions in [Ta/CoFeB/MgO]_n multilayers. First, by using ptychography, a high‐resolution diffraction imaging technique, the 2D out‐of‐plane spin profile of skyrmions with a spatial resolution of 10 nm is determined. Second, by performing circular dichroism in resonant elastic X‐ray scattering, it is demonstrated that the chirality of the magnetic structure undergoes a depth‐dependent evolution. This suggests that the skyrmion structure is a complex 3D structure rather than an identical planar texture throughout the layer stack. The analyses of the spin textures confirm the theoretical predictions that the dipole–dipole interactions together with the external magnetic field play an important role in stabilizing sub‐100 nm diameter skyrmions and the hybrid structure of the skyrmion domain wall. This combined X‐ray‐based approach opens the door for in‐depth studies of magnetic skyrmion systems, which allows for precise engineering of optimized skyrmion heterostructures.     

Investigation of the thermal and structural properties of single-molecule magnet/polymer nanocomposite films

The inclusion of manganese-based single-molecule magnets (SMMs) into solvent cast films of poly(methyl methacrylate) (PMMA) or polycarbonate (PC) was found to influence the thermal stability of these polymers. Examination of the thermal decomposition profiles of PMMA films by thermo-gravimetric analysis (TGA) established that increasing weight % of SMM results in both enhancement of the rate of decomposition initiated at “head-to-head” linkages along with suppression of the rate of decomposition initiated at vinylidene chain ends. In the case of PC films, the temperature at which the primary thermal decomposition occurs decreases with increasing weight % of SMM. The extent of these decomposition trends is correlated to the degree of SMM dispersal, as studied by transmission electron microscopy (TEM). Favourable interactions between the ligands coordinated to the SMMs and the polymer or solvent used in film preparation dictated the degree of SMM dispersal, with the ligand–polymer interactions being dominant on the nano-length scale (1–100 nm) and ligand–solvent interactions being dominant on the micro-length scale (>100 nm).     

Evidence of Spin Frustration in a Vanadium Diselenide Monolayer Magnet

Monolayer VSe₂, featuring both charge density wave and magnetism phenomena, represents a unique van der Waals magnet in the family of metallic 2D transition‐metal dichalcogenides (2D‐TMDs). Herein, by means of in situ microscopy and spectroscopic techniques, including scanning tunneling microscopy/spectroscopy, synchrotron X‐ray and angle‐resolved photoemission, and X‐ray absorption, direct spectroscopic signatures are established, that identify the metallic 1T‐phase and vanadium 3d¹ electronic configuration in monolayer VSe₂ grown on graphite by molecular‐beam epitaxy. Element‐specific X‐ray magnetic circular dichroism, complemented with magnetic susceptibility measurements, further reveals monolayer VSe₂ as a frustrated magnet, with its spins exhibiting subtle correlations, albeit in the absence of a long‐range magnetic order down to 2 K and up to a 7 T magnetic field. This observation is attributed to the relative stability of the ferromagnetic and antiferromagnetic ground states, arising from its atomic‐scale structural features, such as rotational disorders and edges. The results of this study extend the current understanding of metallic 2D‐TMDs in the search for exotic low‐dimensional quantum phenomena, and stimulate further theoretical and experimental studies on van der Waals monolayer magnets.     

Cellulose‐Based Microparticles for Magnetically Controlled Optical Modulation and Sensing

Responsive materials with birefringent optical properties have been exploited for the manipulation of light in several modern electronic devices. While electrical fields are often utilized to achieve optical modulation, magnetic stimuli may offer an enticing complementary approach for controlling and manipulating light remotely. Here, the synthesis and characterization of magnetically responsive birefringent microparticles with unusual magneto‐optical properties are reported. These functional microparticles are prepared via a microfluidic emulsification process, in which water‐based droplets are generated in a flow‐focusing device and stretched into anisotropic shapes before conversion into particles via photopolymerization. Birefringence properties are achieved by aligning cellulose nanocrystals within the microparticles during droplet stretching, whereas magnetic responsiveness results from the addition of superparamagnetic nanoparticles to the initial droplet template. When suspended in a fluid, the microparticles can be controllably manipulated via an external magnetic field to result in unique magneto‐optical coupling effects. Using a remotely actuated magnetic field coupled to a polarized optical microscope, these microparticles can be employed to convert magnetic into optical signals or to estimate the viscosity of the suspending fluid through magnetically driven microrheology.     

High Energy and High Coercivity Sintered NdFeB Magnets by Low Oxygen Process

1. IntroductionSince NdFeB magnets were discovered[ll, theirmagnetic performance has been improved by many researchers. The maximum energy product of sinteredNdFeB magnets has been increased from 240 kJ/m'to 430 kJ/m' by Kaneko et al.[2] in 1993. The maximtun energy product commercially available todayis close to 358 kJ/m'. Because of this high performance of NdFeB products, the applications have increased enormously in the last decade. For example,hard disk drivers (HDD), magnetic reso…     

纳米复相Nd-Fe-B磁体永磁材料发展新方向

探讨了纳米复相Nd-Fe-B磁体的理论依据,总结了这种材料的种类、制备工艺以及提高材料磁性能的方法。最后对这种材料的应用前景进行了展望。     

FePt Hard Magnets

The FePt alloys have recently attracted considerable attention due to their excellent intrinsic magnetic, chemical and mechanical properties. Their possible usage ranges from permanent magnets for special applications (e.g. in micro‐electro‐mechanical systems, magnetic MEMS, and in aggressive environments) to ultra‐high density magnetic storage media. The article describes general aspects concerning the phase formation and magnetic properties of materials based on the L1₀ FePt phase. Both thin film and bulk approaches are considered. The production of bulk nanocrystalline Fe_100‐xPt_x powders by mechanical alloying and subsequent annealing is described. Various combinations of phases, away from thermodynamic equilibrium, have been obtained using this technique.     

Local magnetic properties of a monolayer of Mn12 single molecule magnets

The magnetic properties of a monolayer of Mn12 single molecule magnets grafted onto a silicon (Si) substrate have been investigated using depth-controlled beta-detected nuclear magnetic resonance. A low-energy beam of spin-polarized radioactive 8Li was used to probe the local static magnetic field distribution near the Mn12 monolayer in the Si substrate. The resonance line width varies strongly as a function of implantation depth as a result of the magnetic dipolar fields generated by the Mn12 electronic magnetic moments. The temperature dependence of the line width indicates that the magnetic properties of the Mn12 moments in this low-dimensional configuration differ from bulk Mn12.     

粘结Ni52Mn24.4Ga23.6磁体研究

真空感应熔炼法制备了多晶Ni52Mn24.4Ga23.6合金,对多晶合金进行了DSC分析和显微组织观察;采用粉末压缩压制的方法制备了粘结Ni52Mn24.4Ga23.6磁体;通过X射线衍射分析,讨论了外应力场和磁场对粘结Ni52Mn24.4Ga23.6磁体马氏体相变的影响;测量了粘结Ni52Mn24.4Ga23.6磁体在磁场下的磁诱发应变.结果表明:室温时粘结磁体在1.2T的磁场下能产生150ppm的饱和伸长应变.     

Charged polaron-enhanced circular dichroism of optically nonlinear 3-nitroaniline crystal

The circular dichroism (CD) spectra in visible range of the 3-nitroaniline (m-NA) single crystal, of its solution in chloroform, and in the KBr pellet were recorded. Neither the molecular (m or C_s) nor the crystal (mm2 or C_2v) point groups belong to the chiral groups. The DFT calculation of CD spectrum of the m-NA isolated neutral molecule confirmed its chirality. The red shifted bands in the calculated CD spectrum of m-NA radical anion (charged polaron), as compared with the neutral molecule, resemble better the spectra of solids than that of the solution. It seems that these facts corroborate qualitatively the “hop and turn” model explaining the m-NA optical nonlinearity and electric conductivity proposed in Szostak et al. [M.M. Szostak, H. Chojnacki, E. Staryga, M. D?u?niewski, G. B?k, Chem. Phys. 365 (2009) 44-52].     

回收制备烧结Nd-Fe-B磁体的磁性能与耐热性能

以废旧钕铁硼磁体为原料,采用短流程回收制备技术制备了烧结Nd-Fe-B磁体,通过添加镨钕混合稀土研究了磁体的磁性能和耐热性能.结果表明,在回收磁体中添加2％ PrNd,制备的烧结Nd-Fe-B磁体的剩磁为1.31T、矫顽力为1 474.86 kA/m、磁能积为353.90 kJ/m3.与一次成品相比矫顽力恢复到102％,剩磁恢复到95％,磁能积恢复到90％.在293～393 K范围内未掺杂PrNd磁体的矫顽力温度系数为-0.589 9％/K,掺杂2％PrNd磁体的矫顽力温度系数为-0.556 4％/K,提高了磁体在高温下的耐热性能.这是由于添加混合稀土PrNd增强了主相晶粒间的去磁交换耦合作用,提高了主相的磁晶各向异性场,从而提高了磁体的矫顽力和耐热性能.     

Self‐Assembly of TbPc2 Single‐Molecule Magnets on Surface through Multiple Hydrogen Bonding

The complexation between 2‐ureido‐4[1H]‐pyrimidinone (UPy) and 2,7‐diamido‐1,8‐naphthyridine (NaPy) is used to promote the mild chemisorption of a UPy‐functionalized terbium(III) double decker system on a silicon surface. The adopted strategy allows the single‐molecule magnet behavior of the system to be maintained unaltered on the surface.     

Computational Design of Rare-Earth Reduced Permanent Magnets

Multiscale simulation is a key research tool in the quest for new permanent magnets. Starting with first principles methods, a sequence of simulation methods can be applied to calculate the maximum possible coercive field and expected energy density product of a magnet made from a novel magnetic material composition. Iron (Fe)-rich magnetic phases suitable for permanent magnets can be found by means of adaptive genetic algorithms. The intrinsic properties computed by ab initio simulations are used as input for micromagnetic simulations of the hysteresis properties of permanent magnets with a realistic structure. Using machine learning techniques, the magnet’s structure can be optimized so that the upper limits for coercivity and energy density product for a given phase can be estimated. Structure property relations of synthetic permanent magnets were computed for several candidate hard magnetic phases. The following pairs (coercive field (T), energy density product (kJ·m⁻³)) were obtained for iron-tin-antimony (Fe₃Sn_0.75Sb_0.25): (0.49, 290), L1₀-ordered iron-nickel (L1₀ FeNi): (1, 400), cobalt-iron-tantalum (CoFe₆Ta): (0.87, 425), and manganese-aluminum (MnAl): (0.53, 80).     

Structure and Microscopic Magnetism of Epitaxial Ni–Mn–Ga Films

We report on the structural and magnetic properties of epitaxial thin films of the ferromagnetic shape memory material Ni–Mn–Ga prepared by DC magnetron sputter deposition. Different substrate materials, i.e., MgO(100) and Al₂O₃(11?20) allow for a tailored epitaxial growth. Using a sacrificial chromium buffer layer freestanding epitaxial films are obtained. In combination with photolithography partially freestanding structures such as microbridges are fabricated. The complex martensite crystal structure in substrate‐constrained and freestanding films is studied by means of X‐ray diffraction. The identified asymmetric twin variant configuration is associated with a macroscopic surface pattern observed by optical microscopy. The absence of magnetic‐field induced strain in the (100) oriented samples is explained on basis of the detected twin variant configuration using a simplified model. Taking advantage of the thin film geometry spectroscopic methods are applied to the samples. The measurements provide the first experimental test for changes in the electronic structure of the involved 3d metals during a martensitic transition. Exploiting the X‐ray magnetic circular dichroism quantitative information on the element‐specific spin and orbital magnetic moments are accessed. In addition, angular‐dependent experiments allow us to trace the microscopic origin of the magnetic anisotropy in Ni₂MnGa improving the fundamental understanding of this material.