Tunable Magnetism in Atomically Thin Itinerant Antiferromagnet with Room-Temperature Ferromagnetic Order.

Addressing the need for modulated spin configurations is crucial, as they serve as the foundational building blocks for next-generation spintronics, particularly in atomically thin structures and at room temperature. In this work, we realize intrinsic ferromagnetism in monolayer flakes and tunable ferro-/antiferromagnetism in (Fe0.56Co0.44)5GeTe2 antiferromagnets. Remarkably, the ferromagnetic ordering (≥1 L) and antiferromagnetic ordering (≥4 L) remain discernible up to room temperature. The TC (∼310 K) of the monolayer flakes sets a record high for known exfoliated monolayer van der Waals magnets. Within the framework of A-type antiferromagnetism, a notable odd-even layer-number effect at elevated temperatures (T = 150 K) is observed. Of particular interest is the strong ferromagnetic order in even-layer flakes at low temperatures. The intricate interplay among magnetic field strength, layer number, and temperature gives rise to a diverse array of phenomena, holding promise not only for new physics but also for practical applications.

Tracking Coordination Environment and Reaction Intermediates in Homogeneous and Heterogeneous Epoxidation Catalysts via Ti L2,3-Edge Near-Edge X-ray Absorption Fine Structures.

Ti-based molecules and materials are ubiquitous and play a major role in both homogeneous and heterogeneous catalytic processes. Understanding the electronic structures of their active sites (oxidation state, local symmetry, and ligand environment) is key to developing molecular-level structure-property relationships. In that context, X-ray absorption spectroscopy (XAS) offers a unique combination of elemental selectivity and sensitivity to local symmetry. Commonly, for early transition metals such as Ti, K-edge XAS is applied for in situ characterization and subsequent structural analysis with high sensitivity toward tetrahedral species. Ti L2,3-edge spectroscopy is in principle complementary and offers specific opportunities to interrogate the electronic structure of five-and six-coordinated species. It is, however, much more rarely implemented because the use of soft X-rays implies ultrahigh vacuum conditions. Furthermore, the interpretation of the data can be challenging. Here, we show how Ti L2,3-edge spectroscopy can help to obtain unique information about both homogeneous and heterogeneous epoxidation catalysts and develop a molecular-level relationship between spectroscopic signatures and electronic structures. Toward this goal, we first establish a spectral library of molecular Ti reference compounds, comprising various coordination environments with mono- and dimeric Ti species having O, N, and Cl ligands. We next implemented a computational methodology based on multiplet ligand field theory and maximally localized Wannier orbitals benchmarked on our library to understand Ti L2,3-edge spectroscopic signatures. We finally used this approach to track and predict the spectra of catalytically relevant intermediates, focusing on Ti-based olefin epoxidation catalysts.

Charge Transfer and Orbital Reconstruction at an Organic-Oxide Interface.

The two-dimensional electron system (2DES) located at the surface of strontium titanate (STO) and at several other STO-based interfaces has been an established platform for the study of novel physical phenomena since its discovery. Here we report how the interfacing of STO and tetracyanoquinodimethane (TCNQ) results in a charge transfer that depletes the number of free carriers at the STO surface, with a strong impact on its electronic structure. Our study paves the way for efficient tuning of the electronic properties, which promises novel applications in the framework of oxide/organic-based electronics.

Correlation between Electronic Configuration and Magnetic Stability in Dysprosium Single Atom Magnets.

Single atom magnets offer the possibility of magnetic information storage in the most fundamental unit of matter. Identifying the parameters that control the stability of their magnetic states is crucial to design novel quantum magnets with tailored properties. Here, we use X-ray absorption spectroscopy to show that the electronic configuration of dysprosium atoms on MgO(100) thin films can be tuned by the proximity of the metal Ag(100) substrate onto which the MgO films are grown. Increasing the MgO thickness from 2.5 to 9 monolayers induces a change in the dysprosium electronic configuration from 4f9 to 4f10. Hysteresis loops indicate long magnetic lifetimes for both configurations, however, with a different field-dependent magnetic stability. Combining these measurements with scanning tunneling microscopy, density functional theory, and multiplet calculations unveils the role of the adsorption site and charge transfer to the substrate in determining the stability of quantum states in dysprosium single atom magnets.

Substrate-Independent Magnetic Bistability in Monolayers of the Single-Molecule Magnet Dy2 ScN@C80 on Metals and Insulators.

Magnetic hysteresis is demonstrated for monolayers of the single-molecule magnet (SMM) Dy2 ScN@C80 deposited on Au(111), Ag(100), and MgO|Ag(100) surfaces by vacuum sublimation. The topography and electronic structure of Dy2 ScN@C80 adsorbed on Au(111) were studied by STM. X-ray magnetic CD studies show that the Dy2 ScN@C80 monolayers exhibit similarly broad magnetic hysteresis independent on the substrate used, but the orientation of the Dy2 ScN cluster depends strongly on the surface. DFT calculations show that the extent of the electronic interaction of the fullerene molecules with the surface is increasing dramatically from MgO to Au(111) and Ag(100). However, the charge redistribution at the fullerene-surface interface is fully absorbed by the carbon cage, leaving the state of the endohedral cluster intact. This Faraday cage effect of the fullerene preserves the magnetic bistability of fullerene-SMMs on conducting substrates and facilitates their application in molecular spintronics.

Multimodeling Approach to Ferromagnetic Spin-Wave Excitations in the High-Spin Cluster Mn18Sr Observed by Inelastic Neutron Scattering.

The magnetism of the mixed-valence high-spin cluster [Mn18SrO8(N3)7Cl(MedhmpH)12(MeCN)6]Cl2 (1) exhibiting intramolecular ferromagnetic interactions was studied using inelastic neutron scattering (INS), and reliable values for the exchange coupling constants were determined based on the quality of simultaneous fits to the INS and magnetic data. The challenge of the huge size of the Hilbert space (3 375 000) and many exchange coupling constants (7 assuming a C3 symmetry) generally encountered in large spin clusters was resolved as follows: (a) The results of the restricted Hilbert space ferromagnetic cluster spin wave theory were compared to the experimental spectroscopic data. The observed INS transitions were thus assigned to spin wave excitations in a bounded ferromagnetic spin cluster and moreover could be visualized in a straightforward way based on this theory. (b) Simultaneously, Quantum Monte Carlo (QMC) calculations of the temperature-dependent magnetic susceptibility with the same parameter set were compared to the experimental data. Application of state-of-the-art QMC algorithms, as available in the open source ALPS package, in ferromagnetic clusters avoids the full Hamiltonian diagonalization without sacrificing calculation accuracy of the magnetic susceptibility down to the lowest temperatures, which was crucial for the successful analysis. The combined fits revealed two exchange-coupling models with equally good overall agreement to the data. Our preferred model was inspired by magnetostructural correlations and is consistent with them. The model involves three different exchange interactions, one describing the interaction between the core MnIII spins Ja = 14.3(1.0) K and two interactions linking the core and the peripheral MnII spins: Jb = 8.3(4) K and J6 = 3.6(4) K. The use of open-source QMC software and our systematic approach to fitting multiple sets of data obtained by different experimental techniques are described in detail and are generally applicable for understanding large ferromagnetically coupled clusters.

Stability of metallo-porphyrin networks under oxygen reduction and evolution conditions in alkaline media.

Transition metal atoms stabilised by organic ligands or as oxides exhibit promising catalytic activity for the electrocatalytic reduction and evolution of oxygen. Built-up from earth-abundant elements, they offer affordable alternatives to precious-metal based catalysts for application in fuel cells and electrolysers. For the understanding of a catalyst's activity, insight into its structure on the atomic scale is of highest importance, yet commonly challenging to experimentally access. Here, the structural integrity of a bimetallic iron tetrapyridylporphyrin with co-adsorbed cobalt electrocatalyst on Au(111) is investigated using scanning tunneling microscopy and X-ray absorption spectroscopy. Topographic and spectroscopic characterization reveals structural changes of the molecular coordination network after oxygen reduction, and its decomposition and transformation into catalytically active Co/Fe (oxyhydr)oxide during oxygen evolution. The data establishes a structure-property relationship for the catalyst as a function of electrochemical potential and, in addition, highlights how the reaction direction of electrochemical interconversion between molecular oxygen and hydroxyl anions can have very different effects on the catalyst's structure.

Nanoscale x-ray investigation of magnetic metallofullerene peapods.

Endohedral lanthanide ions packed inside carbon nanotubes (CNTs) in a one-dimensional assembly have been studied with a combination of high resolution transmission electron microscopy (HRTEM), scanning transmission x-ray microscopy (STXM), and x-ray magnetic circular dichroism (XMCD). By correlating HRTEM and STXM images we show that structures down to 30 nm are resolved with chemical contrast and record x-ray absorption spectra from endohedral lanthanide ions embedded in individual nanoscale CNT bundles. XMCD measurements of an Er3N@C80 bulk sample and a macroscopic assembly of filled CNTs indicate that the magnetic properties of the endohedral Er3+ ions are unchanged when encapsulated in CNTs. This study demonstrates the feasibility of local magnetic x-ray characterisation of low concentrations of lanthanide ions embedded in molecular nanostructures.

Magnetic Hysteresis in Er Trimers on Cu(111).

We report magnetic hysteresis in Er clusters on Cu(111) starting from the size of three atoms. Combining X-ray magnetic circular dichroism, scanning tunneling microscopy, and mean-field nucleation theory, we determine the size-dependent magnetic properties of the Er clusters. Er atoms and dimers are paramagnetic, and their easy magnetization axes are oriented in-plane. In contrast, trimers and bigger clusters exhibit magnetic hysteresis at 2.5 K with a relaxation time of 2 min at 0.1 T and out-of-plane easy axis. This appearance of magnetic stability for trimers coincides with their enhanced structural stability.

Superlattice of Single Atom Magnets on Graphene.

Regular arrays of single atoms with stable magnetization represent the ultimate limit of ultrahigh density storage media. Here we report a self-assembled superlattice of individual and noninteracting Dy atoms on graphene grown on Ir(111), with magnetic hysteresis up to 5.6 T and spin lifetime of 1000 s at 2.5 K. The observed magnetic stability is a consequence of the intrinsic low electron and phonon densities of graphene and the 6-fold symmetry of the adsorption site. Our array of single atom magnets has a density of 115 Tbit/inch2, defined by the periodicity of the graphene moiré pattern.

Cyanide Single-Molecule Magnets Exhibiting Solvent Dependent Reversible "On" and "Off" Exchange Bias Behavior.

The syntheses, structures, and magnetic properties of four new complex salts, (PPN){[Mn(III)(salphen)(MeOH)]2[M(III)(CN)6]}·7MeOH (Mn2M·7MeOH) (M = Fe, Ru, Os and Co; PPN(+) = bis(triphenylphosphoranylidene)ammonium cation; H2salphen = N,N'-bis(salicylidene)-1,2-diaminobenzene), and a mixed metal Co/Os analogue (PPN){[Mn(III)(salphen)(MeOH)]2[Co(III)0.92Os(III)0.08(CN)6]}·7MeOH were undertaken. It was found that all compounds exhibit switchable single-molecule magnet (SMM) and exchange-bias behavior depending on the interstitial methanol content. The pristine (PPN){[Mn(salphen)(MeOH)]2[Os(CN)6]}·7MeOH (Mn2Os·7MeOH) behaves as an SMM with an effective barrier for the magnetization reversal, (Ueff/kB), of 17.1 K. Upon desolvation, Mn2Os exhibits an increase of Ueff/kB to 42.0 K and an opening of the hysteresis loop observable at 1.8 K. Mn2Os·7MeOH shows also exchange-bias behavior with magnetic hysteresis loops exhibiting a shift in the quantum tunneling to 0.25 T from zero-field. The Fe(III) and Ru(III) analogues were prepared as reference compounds for assessing the effect of the 5d versus 4d and 3d metal ions on the SMM properties. These compounds are also SMMs and exhibit similar effects but with lower energy barriers. These findings underscore the importance of introducing heavy transition elements into SMMs to improve their slow relaxation of the magnetization properties. The (PPN){[Mn(III)(salphen)(MeOH)]2[Co(III)(CN)6]}·7MeOH (Mn2Co·7MeOH) analogue with a diamagnetic Co(III) central atom and the mixed Co/Os (PPN){[Mn(III)(salphen)(MeOH)]2[Co(III)0.92Os(III)0.08(CN)6]}·7MeOH (Mn2Co/Os·7MeOH) "magnetically diluted" system with a 9:1 Co/Os metal ratio were prepared in order to further probe the nature of the energy barrier increase upon desolvation of Mn2Os. In addition, inelastic neutron scattering and frequency-domain Fourier-transform THz electron paramagnetic resonance spectra obtained on Mn2Os·7MeOH and Mn2Os in combination with the magnetic data revealed the presence of anisotropic exchange interactions between Mn(III) and Os(III) ions.

Surface aligned magnetic moments and hysteresis of an endohedral single-molecule magnet on a metal.

The interaction between the endohedral unit in the single-molecule magnet Dy_{2}ScN@C_{80} and a rhodium (111) substrate leads to alignment of the Dy 4f orbitals. The resulting orientation of the Dy_{2}ScN plane parallel to the surface is inferred from comparison of the angular anisotropy of x-ray absorption spectra and multiplet calculations in the corresponding ligand field. The x-ray magnetic circular dichroism is also angle dependent and signals strong magnetocrystalline anisotropy. This directly relates geometric and magnetic structure. Element specific magnetization curves from different coverages exhibit hysteresis at a sample temperature of ∼4 K. From the measured hysteresis curves, we estimate the zero field remanence lifetime during x-ray exposure of a submonolayer to be about 30 seconds.

Design of Single-Molecule Magnets: Insufficiency of the Anisotropy Barrier as the Sole Criterion.

Determination of the electronic energy spectrum of a trigonal-symmetry mononuclear Yb(3+) single-molecule magnet (SMM) by high-resolution absorption and luminescence spectroscopies reveals that the first excited electronic doublet is placed nearly 500 cm(-1) above the ground one. Fitting of the paramagnetic relaxation times of this SMM to a thermally activated (Orbach) model {τ = τ0 × exp[ΔOrbach/(kBT)]} affords an activation barrier, ΔOrbach, of only 38 cm(-1). This result is incompatible with the spectroscopic observations. Thus, we unambiguously demonstrate, solely on the basis of experimental data, that Orbach relaxation cannot a priori be considered as the main mechanism determining the spin dynamics of SMMs. This study highlights the fact that the general synthetic approach of optimizing SMM behavior by maximization of the anisotropy barrier, intimately linked to the ligand field, as the sole parameter to be tuned, is insufficient because of the complete neglect of the interaction of the magnetic moment of the molecule with its environment. The Orbach mechanism is expected dominant only in the cases in which the energy of the excited ligand field state is below the Debye temperature, which is typically low for molecular crystals and, thus, prevents the use of the anisotropy barrier as a design criterion for the realization of high-temperature SMMs. Therefore, consideration of additional design criteria that address the presence of alternative relaxation processes beyond the traditional double-well picture is required.

The metallofullerene field-induced single-ion magnet HoSc2 N@C80.

The low-temperature magnetic properties of the endohedral metallofullerene HoSc2 N@C80 have been studied by superconducting quantum interference device (SQUID) magnetometry. Alternating current (ac) susceptibility measurements reveal that this molecule exhibits slow relaxation of magnetization in a small applied field with timescales in the order of milliseconds. The equilibrium magnetic properties of HoSc2 N@C80 indicate strong magnetic anisotropy. The large differences in magnetization relaxation times between the present compound and the previously investigated DySc2 N@C80 are discussed.

Ferromagnetic Order in 2D Layers of Transition Metal Dichlorides.

Magnetism in two dimensions is traditionally considered an exotic phase mediated by spin fluctuations, but far from collinearly ordered in the ground state. Recently, 2D magnetic states have been discovered in layered van der Waals compounds. Their robust and tunable magnetic state by material composition, combined with reduced dimensionality, foresee a strong potential as a key element in magnetic devices. Here, a class of 2D magnets based on metallic chlorides is presented. The magnetic order survives on top of a metallic substrate, even down to the monolayer limit, and can be switched from perpendicular to in-plane by substituting the metal ion from iron to nickel. Using functionalized STM tips as magnetic sensors, local exchange fields are identified, even in the absence of an external magnetic field. Since the compounds are processable by molecular beam epitaxy techniques, they provide a platform with large potential for incorporation into current device technologies.

Three-axis anisotropic exchange coupling in the single-molecule magnets NEt4[Mn(III)2(5-Brsalen)2(MeOH)2M(III)(CN)6] (M=Ru, Os).

We have investigated the single-molecule magnets [Mn(III)2 (5-Brsalen)2 (MeOH)2 M(III) (CN)6 ]NEt4 (M=Os (1) and Ru (2); 5-Brsalen=N,N'-ethylenebis(5-bromosalicylidene)iminate) by frequency-domain Fourier-transform terahertz electron paramagnetic resonance (THz-EPR), inelastic neutron scattering, and superconducting quantum interference device (SQUID) magnetometry. The combination of all three techniques allows for the unambiguous experimental determination of the three-axis anisotropic magnetic exchange coupling between Mn(III) and Ru(III) or Os(III) ions, respectively. Analysis by means of a spin-Hamiltonian parameterization yields excellent agreement with all experimental data. Furthermore, analytical calculations show that the observed exchange anisotropy is due to the bent geometry encountered in both 1 and 2, whereas a linear geometry would lead to an Ising-type exchange coupling.

Surface-Mediated Spin Locking and Thermal Unlocking in a 2D Molecular Array.

Molecule-based functional devices may take advantage of surface-mediated spin state bistability. Whereas different spin states in conventional spin crossover complexes are only accessible at temperatures well below room temperature, and the lifetimes of the high-spin state are relatively short, a different behavior exhibited by prototypical nickel phthalocyanine is shown here. Direct interaction of the organometallic complex with a copper metal electrode mediates the coexistence of a high spin and a low spin state within the 2D molecular array. The spin state bistability is extremely non-volatile, since no external stimuli are required to preserve it. It originates from the surface-induced axial displacement of the functional nickel cores, which generates two stable local minima. Spin state unlocking and the full conversion to the low spin state are only possible by a high temperature stimulus. This spin state transition is accompanied by distinct changes in the molecular electronic structure that might facilitate the state readout at room temperature, as evidenced by valence spectroscopy. The non-volatility of the high spin state up to elevated temperatures and the controllable spin bistability render the system extremely intriguing for applications in molecule-based information storage devices.

An endohedral single-molecule magnet with long relaxation times: DySc2N@C80.

The magnetism of DySc(2)N@C(80) endofullerene was studied with X-ray magnetic circular dichroism (XMCD) and a magnetometer with a superconducting quantum interference device (SQUID) down to temperatures of 2 K and in fields up to 7 T. XMCD shows hysteresis of the 4f spin and orbital moment in Dy(III) ions. SQUID magnetometry indicates hysteresis below 6 K, while thermal and nonthermal relaxation is observed. Dilution of DySc(2)N@C(80) samples with C(60) increases the zero-field 4f electron relaxation time at 2 K to several hours.

X-Treme beamline at SLS: X-ray magnetic circular and linear dichroism at high field and low temperature.

X-Treme is a soft X-ray beamline recently built in the Swiss Light Source at the Paul Scherrer Institut in collaboration with École Polytechnique Fédérale de Lausanne. The beamline is dedicated to polarization-dependent X-ray absorption spectroscopy at high magnetic fields and low temperature. The source is an elliptically polarizing undulator. The end-station has a superconducting 7 T-2 T vector magnet, with sample temperature down to 2 K and is equipped with an in situ sample preparation system for surface science. The beamline commissioning measurements, which show a resolving power of 8000 and a maximum flux at the sample of 4.7 × 10(12) photons s(-1), are presented. Scientific examples showing X-ray magnetic circular and X-ray magnetic linear dichroism measurements are also presented.

X-ray magnetic circular dichroism (XMCD) study of a methoxide-bridged Dy(III)-Cr(III) cluster obtained by fluoride abstraction from cis-[Cr(III)F2(phen)2](+).

An isostructural series of dinuclear chromium(III)-lanthanide(III) clusters is formed by fluoride abstraction of cis-[CrF2(phen)2](+) by Ln(3+) resulting in LnF3 and methoxide-bridged Cr-Ln clusters (Ln = Nd (1), Tb (2), Dy (3)) of formula [Cr(III)(phen)2(µ-MeO)2Ln(NO3)4]·xMeOH (x = 2-2.73). In contrast to fluoride, methoxide bridges in a nonlinear fashion, which facilitates chelation. For 3, X-ray magnetic circular dichroism (XMCD) provides element-specific magnetization curves that are compared to cluster magnetization and susceptibility data acquired by SQUID magnetometry. The combination of XMCD and SQUID is able to resolve very small magnetic coupling values and reveals a weak Cr(III)-Dy(III) coupling of j = -0.04(3) cm(-1). The Dy(III) ion has a ground-state Kramers doublet of mJ = ±13/2, and the first excited doublet is found to be mJ = ±11/2 at an energy of δ = 57(21) cm(-1). The Cr(III) ion exhibits a uniaxial anisotropy of DCr = -1.7(1.0) cm(-1). Further, we observe that a weak anisotropic coupling of dipolar origin is sufficient to model the data, suggesting that methoxide bridges do not play a significant role in the magnetic coupling for the present systems.