Temperature Induced Reversible Switching of the Magnetic Anisotropy in a Neodymium Complex Adsorbed on Graphite.

Controlling the magnetic anisotropy of molecular layers assembled on a surface is one of the challenges that needs to be addressed to create the next-generation spintronic devices. Recently, metal complexes that show a reversible solid-state switch of their magnetic anisotropy in response to physical stimuli, such as temperature and magnetic field, have been discovered. The complex Nd(trensal) (H3trensal = 2,2',2''-tris(salicylideneimino)triethylamine) is predicted to exhibit such property. An ultra-thin film of Nd(trensal) is deposited on highly ordered pyrolytic graphite as a proof-of-concept system to show that this property can be retained at the nanoscale on a layered material. By combining single crystal magnetometric measurements and synchrotron X-ray-based absorption techniques, supported by multiplet ligand field simulations based on the trigonal crystal field surrounding the lanthanide centre, it is demonstrated that changing the temperature reverses the magnetic anisotropy of an ordered film of Nd(trensal), thus opening significant perspectives for the realization of a novel family of temperature-controlled molecular spintronic devices.

Hybrid Heterostructures of a Spin Crossover Coordination Polymer on MoS2 : Elucidating the Role of the 2D Substrate.

Controlling the deposition of spin-crossover (SCO) materials constitutes a crucial step for the integration of these bistable molecular systems in electronic devices. Moreover, the influence of functional surfaces, such as 2D materials, can be determinant on the properties of the deposited SCO film. In this work, ultrathin films of the SCO Hofmann-type coordination polymer [Fe(py)2 {Pt(CN)4 }] (py = pyridine) onto monolayers of 1T and 2H MoS2 polytypes are grown. The resulting hybrid heterostructures are characterized by GIXRD, XAS, XPS, and EXAFS to get information on the structure and the specific interactions generated at the interface, as well as on the spin transition. The use of a layer-by-layer results in SCO/2D heterostructures, with crystalline and well-oriented [Fe(py)2 {Pt(CN)4 }]. Unlike with conventional Au or SiO2 substrates, no intermediate self-assembled monolayer is required, thanks to the surface S atoms. Furthermore, it is observed that the higher presence of Fe3+ in the 2H heterostructures hinders an effective spin transition for [Fe(py)2 {Pt(CN)4 }] films thinner than 8 nm. Remarkably, when using 1T MoS2 , this transition is preserved in films as thin as 4 nm, due to the reducing character of this metallic substrate. These results highlight the active role that 2D materials play as substrates in hybrid molecular/2D heterostructures.

Orbital Magnetic Moment and Single-Ion Magnetic Anisotropy of the S = 1/2 K3[Fe(CN)6] Compound: A Case Where the Orbital Magnetic Moment Dominates the Spin Magnetic Moment.

The potassium hexacyanoferrate(III), K3[FeIII(CN)6], is known for its exceptional magnetic anisotropy among the 3d transition metal series. The Fe(III) ions are in the S = 1/2 low spin state imposed by the strong crystal field of the cyanido ligands. A large orbital magnetic moment is expected from previous publications. In the present work, X-ray magnetic circular dichroism was recorded for a powder sample, allowing direct measurement of the Fe(III) orbital magnetic moment. A combination of molecular multiconfigurational ab initio and atomic ligand field multiplets calculations provides the spin and orbital magnetic moments for the [FeIII(CN)6]3- isolated cluster, the crystallographic unit cell, and the powder sample. The calculations of the angular dependencies of the spin and orbital magnetic moments with the external magnetic induction direction reveal easy magnetization axes for each S = 1/2 molecular entity and the crystal. It also shows that the orbital magnetic moment dominates the spin magnetic moment for all directions. Our measurements confirm that the orbital magnetic moment contributes to 60% of the total magnetization for the powder, which is in excellent agreement with our theoretical predictions. An orbital magnetic moment greater than the spin magnetic moment is exceptional for 3d transition metal ions. The impact of crystal field strength and distortion, π back-bonding, spin-orbit coupling, and external magnetic induction was analyzed, leading to a deeper understanding of the spin and orbital magnetic anisotropies.

Quantum dynamics of a single molecule magnet on superconducting Pb(111).

Magnetic materials interfaced with superconductors may reveal new physical phenomena with potential for quantum technologies. The use of molecules as magnetic components has already shown great promise, but the diversity of properties offered by the molecular realm remains largely unexplored. Here we investigate a submonolayer of tetrairon(III) propeller-shaped single molecule magnets deposited on a superconducting lead surface. This material combination reveals a strong influence of the superconductor on the spin dynamics of the single molecule magnet. It is shown that the superconducting transition to the condensate state switches the single molecule magnet from a blocked magnetization state to a resonant quantum tunnelling regime. Our results open perspectives to control single molecule magnetism via superconductors and to use single molecule magnets as local probes of the superconducting state.

Magnetic Hysteresis in a Monolayer of Oriented 6 nm CsNiCr Prussian Blue Analogue Nanocrystals.

Prussian blue analogue nanocrystals of the CsINiII[CrIII(CN)6] cubic network with 6 nm size were assembled as a single monolayer on highly organized pyrolytic graphite (HOPG). X-ray magnetic circular dichroism (XMCD) studies, at the Ni and Cr L2,3 edges, reveal the presence of an easy plane of magnetization evidenced by an opening of the magnetic hysteresis loop (coercive field of ≈200 Oe) when the magnetic field, B, is at 60° relative to the normal to the substrate. The angular dependence of the X-ray natural linear dichroism (XNLD) reveals both an orientation of the nanocrystals on the substrate and an anisotropy of the electronic cloud of the NiII and CrIII coordination sphere species belonging to the nanocrystals' surface. Ligand field multiplet (LFM) calculations that reproduce the experimental data are consistent with an elongated tetragonal distortion of surface NiII coordination sphere responsible for the magnetic behavior of monolayer.

Anomalous Light-Induced Spin-State Switching for Iron(II) Spin-Crossover Molecules in Direct Contact with Metal Surfaces.

Light-induced spin-state switching is one of the most attractive properties of spin-crossover materials. In bulk, low-spin (LS) to high-spin (HS) conversion via the light-induced excited spin-state trapping (LIESST) effect may be achieved with a visible light, while the HS-to-LS one (reverse-LIESST) requires an excitation in the near-infrared range. Now, it is shown that those phenomena are strongly modified at the interface with a metal. Indeed, an anomalous spin conversion is presented from HS state to LS state under blue light illumination for FeII spin-crossover molecules that are in direct contact with metallic (111) single-crystal surfaces (copper, silver, and gold). To interpret this anomalous spin-state switching, a new mechanism is proposed for the spin conversion based on the light absorption by the substrate that can generate low energy valence photoelectrons promoting molecular vibrational excitations and subsequent spin-state switching at the molecule-metal interface.

Atomic Scale Evidence of the Switching Mechanism in a Photomagnetic CoFe Dinuclear Prussian Blue Analogue.

Molecular complexes based on Prussian Blue analogues have recently attracted considerable interest for their unique bistable properties combined to ultimately reduced dimensions. Here, we investigate the first dinuclear FeCo complex exhibiting both thermal and photomagnetic bistability in the solid state. Through an experimental and theoretical approach combining local techniques-X-ray absorption spectroscopy (XAS), X-ray magnetic circular dichroism (XMCD), and ligand field multiplet calculations-we were able to evidence the changes occurring at the atomic scale in the electronic and magnetic properties. The spectroscopic studies were able to fully support at the atomic level the following conclusions: (i) the 300 K phase and the light-induced excited state at 4 K are both built from FeLSIII-CoHSII paramagnetic pairs with no apparent reorganization of the local structure, (ii) the 100 K phase is composed of FeLSII-CoLSIII diamagnetic pairs, and (iii) the light-induced excited state is fully relaxed at an average temperature of ≈50 K. In the paramagnetic phase at 2 K, XAS and XMCD reveal that both Fe and Co ions exhibit a rather large orbital magnetic moment (0.65 µB and 0.46 µB, respectively, under an external magnetic induction of 6.5 T), but it was not possible to detect a magnetic interaction between spin centers above 2 K.

Tunable Spin-Superconductor Coupling of Spin 1/2 Vanadyl Phthalocyanine Molecules.

Atomic-scale magnetic moments in contact with superconductors host rich physics based on the emergence of Yu-Shiba-Rusinov (YSR) magnetic bound states within the superconducting condensate. Here, we focus on a magnetic bound state induced into Pb nanoislands by individual vanadyl phthalocyanine (VOPc) molecules deposited on the Pb surface. The VOPc molecule is characterized by a spin magnitude of 1/2 arising from a well-isolated singly occupied d xy-orbital and is a promising candidate for a molecular spin qubit with long coherence times. X-ray magnetic circular dichroism (XMCD) measurements show that the molecular spin remains unperturbed even for molecules directly deposited on the Pb surface. Scanning tunneling spectroscopy and density functional theory (DFT) calculations identify two adsorption geometries for this "asymmetric" molecule (i.e., absence of a horizontal symmetry plane): (a) oxygen pointing toward the vacuum with the Pc laying on the Pb, showing negligible spin-superconductor interaction, and (b) oxygen pointing toward the Pb, presenting an efficient interaction with the Pb and promoting a Yu-Shiba-Rusinov bound state. Additionally, we find that in the first case a YSR state can be induced smoothly by exerting mechanical force on the molecules with the scanning tunneling microscope (STM) tip. This allows the interaction strength to be tuned continuously from an isolated molecular spin case, through the quantum critical point (where the bound state energy is zero) and beyond. DFT indicates that a gradual bending of the VO bond relative to the Pc ligand plane promoted by the STM tip can modify the interaction in a continuously tunable manner. The ability to induce a tunable YSR state in the superconductor suggests the possibility of introducing coupled spins on superconductors with switchable interaction.

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.

Weak Ferromagnetic Interaction at the Surface of the Ferrimagnetic Rb2Co4[Fe(CN)6]3.3·11H2O Photoexcited State.

CoFe Prussian blue analogues (PBAs) are well-known for their magnetic bistability tuned by external stimuli. The photoswitching properties are due to the electron transfer from CoLSIII-NC-FeLSII to CoHSII-NC-FeLSIII linkage, accompanied by the spin change of the Co ions (HS stands for high spin and LS for low spin). In this work, we investigated 100 nm particles of the Rb2Co4[Fe(CN)6]3.3·11H2O PBA (named RbCoFe). The photoexcited state of the PBA was reached by red laser excitation (λ = 635 nm) and observed by X-ray absorption spectroscopy and X-ray magnetic circular dichroism (XMCD) that are element-specific probes. The XMCD measurements at the Co and Fe L2,3 edges, probing the magnetic 3d orbitals, have provided a direct evidence of the antiferromagnetic interaction between the CoHSII and the FeLSIII ions belonging to the core of the particles, thus confirming the previously published, though indirect XMCD measurements at K edges. Because of the surface sensitivity of XMCD at the L2,3 edges, the magnetic properties of the particle surface were also revealed. Surface CoHSII-FeLSIII pairs exhibit a weak ferromagnetic interaction. Thus, the magnetic structure of the photomagnetic RbCoFe 100 nm particles can be described as a ferrimagnetic core surrounded by a ferromagnetic shell. This finding brings new insights into the understanding of the complex magnetic properties of photoexcited RbCoFe and shows that the surface can have different magnetic behavior than the core. This should impact the nature of magnetic coupling in nanoparticles of CoFe PBA, where surface effect will dominate.

Proof of Principle: Immobilisation of Robust CuII3 TbIII -Macrocycles on Small, Suitably Pre-functionalised Gold Nanoparticles.

In a proof-of-principle study, a soluble macrocyclic single-molecule magnet (SMM) containing a CuII3 TbIII magnetic core was covalently grafted onto small gold nanoparticles pre-functionalised with carboxylate-terminated tethers. A modified microemulsion method allowed production of the small and monodisperse nanoparticles (approximately 3.5 nm in diameter) for the chemisorption of a large amount of intact macrocyclic complexes in the hybrid system.

Iron L2,3-Edge X-ray Absorption and X-ray Magnetic Circular Dichroism Studies of Molecular Iron Complexes with Relevance to the FeMoco and FeVco Active Sites of Nitrogenase.

Herein, a systematic study of a series of molecular iron model complexes has been carried out using Fe L2,3-edge X-ray absorption (XAS) and X-ray magnetic circular dichroism (XMCD) spectroscopies. This series spans iron complexes of increasing complexity, starting from ferric and ferrous tetrachlorides ([FeCl4]-/2-), to ferric and ferrous tetrathiolates ([Fe(SR)4]-/2-), to diferric and mixed-valent iron-sulfur complexes [Fe2S2R4]2-/3-. This test set of compounds is used to evaluate the sensitivity of both Fe L2,3-edge XAS and XMCD spectroscopy to oxidation state and ligation changes. It is demonstrated that the energy shift and intensity of the L2,3-edge XAS spectra depends on both the oxidation state and covalency of the system; however, the quantitative information that can be extracted from these data is limited. On the other hand, analysis of the Fe XMCD shows distinct changes in the intensity at both L3 and L2 edges, depending on the oxidation state of the system. It is also demonstrated that the XMCD intensity is modulated by the covalency of the system. For mononuclear systems, the experimental data are correlated with atomic multiplet calculations in order to provide insights into the experimental observations. Finally, XMCD is applied to the tetranuclear heterometal-iron-sulfur clusters [MFe3S4]3+/2+ (M = Mo, V), which serve as structural analogues of the FeMoco and FeVco active sites of nitrogenase. It is demonstrated that the XMCD data can be utilized to obtain information on the oxidation state distribution in complex clusters that is not readily accessible for the Fe L2,3-edge XAS data alone. The advantages of XMCD relative to standard K-edge and L2,3-edge XAS are highlighted. This study provides an important foundation for future XMCD studies on complex (bio)inorganic systems.

Exchange bias and room-temperature magnetic order in molecular layers.

Molecular semiconductors may exhibit antiferromagnetic correlations well below room temperature. Although inorganic antiferromagnetic layers may exchange bias single-molecule magnets, the reciprocal effect of an antiferromagnetic molecular layer magnetically pinning an inorganic ferromagnetic layer through exchange bias has so far not been observed. We report on the magnetic interplay, extending beyond the interface, between a cobalt ferromagnetic layer and a paramagnetic organic manganese phthalocyanine (MnPc) layer. These ferromagnetic/organic interfaces are called spinterfaces because spin polarization arises on them. The robust magnetism of the Co/MnPc spinterface stabilizes antiferromagnetic ordering at room temperature within subsequent MnPc monolayers away from the interface. The inferred magnetic coupling strength is much larger than that found in similar bulk, thin or ultrathin systems. In addition, at lower temperature, the antiferromagnetic MnPc layer induces an exchange bias on the Co film, which is magnetically pinned. These findings create new routes towards designing organic spintronic devices.

Large Orbital Magnetic Moment Measured in the [TpFe(III)(CN)3](-) Precursor of Photomagnetic Molecular Prussian Blue Analogues.

Photomagnetism in three-dimensional Co/Fe Prussian blue analogues is a complex phenomenon, whose detailed mechanism is not yet fully understood. Recently, researchers have been able to prepare molecular fragments of these networks using a building block synthetic approach from mononuclear precursors. The main objective in this strategy is to isolate the smallest units that show an intramolecular electron transfer to have a better understanding of the electronic processes. A prior requirement to the development of this kind of system is to understand to what extent electronic and magnetic properties are inherited from the corresponding precursors. In this work, we investigate the electronic and magnetic properties of the FeTp precursor (N(C4H9)4)[TpFe(III)(CN)3], (Tp being tris-pyrazolyl borate) of a recently reported binuclear cyanido-bridged Fe/Co complex. X-ray absorption spectroscopy and X-ray magnetic circular dichroism measurements at the Fe L2,3 edges (2p → 3d) supported by ligand field multiplet calculations have allowed to determine the spin and orbit magnetic moments. Inaccuracy of the spin sum rule in the case of low-spin Fe(III) ion was demonstrated. An exceptionally large value of the orbital magnetic moment is found (0.9 µB at T = 2 K and B = 6.5 T) that is likely to play an important role in the magnetic and photomagnetic properties of molecular Fe/Co Prussian blue analogues.

Magnetic bistability in a submonolayer of sublimated Fe4 single-molecule magnets.

We demonstrate that Fe4 molecules can be deposited on gold by thermal sublimation in ultra-high vacuum with retention of single molecule magnet behavior. A magnetic hysteresis comparable to that found in bulk samples is indeed observed when a submonolayer film is studied by X-ray magnetic circular dichroism. Scanning tunneling microscopy evidences that Fe4 molecules are assembled in a two-dimensional lattice with short-range hexagonal order and coexist with a smaller contaminant. The presence of intact Fe4 molecules and the retention of their bistable magnetic behavior on the gold surface are supported by density functional theory calculations.

Spin-Dependent Hybridization between Molecule and Metal at Room Temperature through Interlayer Exchange Coupling.

We experimentally and theoretically show that the magnetic coupling at room temperature between paramagnetic Mn within manganese phthalocyanine molecules and a Co layer persists when separated by a Cu spacer. The molecule's magnetization amplitude and direction can be tuned by varying the Cu-spacer thickness and evolves according to an interlayer exchange coupling mechanism. Ab initio calculations predict a highly spin-polarized density of states at the Fermi level of this metal-molecule interface, thereby strengthening prospective spintronics applications.

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.

Room-temperature-persistent magnetic interaction between coordination complexes and nanoparticles in maghemite-based nanohybrids.

Maghemite nanoparticles functionalised with Co(II) coordination complexes at their surface show a significant increase of their magnetic anisotropy, leading to a doubling of the blocking temperature and a sixfold increase of the coercive field. Magnetometric studies suggest an enhancement that is not related to surface disordering, and point to a molecular effect involving magnetic exchange interactions mediated by the oxygen atoms at the interface as its source. Field- and temperature-dependent X-ray absorption spectroscopy (XAS) and X-ray magnetic circular dichroism (XMCD) studies show that the magnetic anisotropy enhancement is not limited to surface atoms and involves the core of the nanoparticle. These studies also point to a mechanism driven by anisotropic exchange and confirm the strength of the magnetic exchange interactions. The coupling between the complex and the nanoparticle persists at room temperature. Simulations based on the XMCD data give an effective exchange field value through the oxido coordination bridge between the Co(II) complex and the nanoparticle that is comparable to the exchange field between iron ions in bulk maghemite. Further evidence of the effectiveness of the oxido coordination bridge in mediating the magnetic interaction at the interface is given with the Ni(II) analog to the Co(II) surface-functionalised nanoparticles. A substrate-induced magnetic response is observed for the Ni(II) complexes, up to room temperature.

Finite size effects on the metamagnetic phase transition in a thick B2 FeRh nanocluster film.

FeRh alloys in the CsCl-type (B2) chemically ordered phase present an antiferromagnetic to ferromagnetic order transition around 370 K observed in bulk and continuous films but absent in nanoclusters. In this study, we investigate the thermal magnetic behavior of a thick film composed of assembled FeRh nanoclusters preformed in the gas phase. This work reveals a broad and asymmetric metamagnetic transition with a consequent residual magnetization at low temperature. Due to the coexistence of different grain sizes in the sample, we confront the results with a description that involves two populations of B2-FeRh particles, and the existence of a discriminating size below which the magnetic order transition does not take place.

Magnetic anisotropy of cyanide-bridged core and core-shell coordination nanoparticles probed by X-ray magnetic circular dichroism.

The local symmetry and local magnetic properties of 6 nm-sized, bimetallic, cyanide-bridged CsNiCr(CN)6 coordination nanoparticles 1 and 8 nm-sized, trimetallic, CsNiCr(CN)6@CsCoCr(CN)6 core-shell nanoparticles 2 were studied by X-ray absorption spectroscopy (XAS) and X-ray magnetic circular dichroism (XMCD). The measurements were performed at the Ni(II), Co(II), and Cr(III) L2,3 edges. This study revealed the presence of distorted Ni(II) sites located on the particle surface of 1 that account for the uniaxial magnetic anisotropy observed by SQUID measurements. For the core-shell particles, a combination of the exchange anisotropy between the core and the shell and the pronounced anisotropy of the Co(II) ions is the origin of the large increase in coercive field from 120 to 890 Oe on going from 1 to 2. In addition, XMCD allows the relative orientation of the magnetic moments throughout the core-shell particles to be determined. While for the bimetallic particles of 1, alignment of the magnetic moments of Cr(III) ions with those of Ni(II) ions leads to uniform magnetization, in the core-shell particles 2 the magnetic moments of the isotropic Cr(III) follow those of Co(II) ions in the shell and those of Ni(II) ions in the core, and this leads to nonuniform magnetization in the whole nanoobject, mainly due to the large difference in local anisotropy between the Co(II) ions belonging to the surface and the Ni(II) ions in the core.