Residual Ferromagnetic Regions Affecting the First-Order Phase Transition in Off-Stoichiometric Fe-Rh.

Among the magnetocaloric materials featuring first-order phase transitions (FOPT), FeRh is considered as a reference system to study the FOPT because it is a "simple" binary system with a CsCl structure exhibiting a large adiabatic temperature change. Recently, ab initio theory predicted that changes in the Fe/Rh stoichiometry in the vicinity of equiatomic composition strongly influence the FOPT characteristics. However, this theoretical prediction was not clearly verified experimentally.

Self-Assembled Tetranuclear Square Complex of Chromium(III) Bridged by Radical Pyrazine: A Molecular Model for Metal-Organic Magnets.

The attractive electronic properties of metal-pyrazine materials─electrical conductivity, magnetic order, and strong magnetic coupling─can be tuned in a wide range depending on the metal employed, as well as its ligand-imposed redox environment. Using solvent-directed synthesis to control the dimensionality of such systems, a discrete tetranuclear chromium(III) complex, exhibiting a rare example of bridging radical pyrazine, has been prepared from chromium(II) triflate and neutral pyrazine. The strong antiferromagnetic interaction between Cr ( = 3/2) and radical pyrazine ( = 1/2) spins, theoretically estimated at about -932 K, leads to a thermally isolated = 4 ground state, which remains the only populated state observable even at 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.

A zero-valent palladium cluster-organic framework.

Acquiring spatial control of nanoscopic metal clusters is central to their function as efficient multi-electron catalysts. However, dispersing metal clusters on surfaces or in porous hosts is accompanied by an intrinsic heterogeneity that hampers detailed understanding of the chemical structure and its relation to reactivities. Tethering pre-assembled molecular metal clusters into polymeric, crystalline 2D or 3D networks constitutes an unproven approach to realizing ordered arrays of chemically well-defined metal clusters.

Stabilization Of The CN Anion In Recoverable High-pressure Ln O (CN ) (Ln=La, Eu, Gd, Tb, Ho, Yb) Oxoguanidinates.

A series of isostructural Ln O (CN ) (Ln=La, Eu, Gd, Tb, Ho, Yb) oxoguanidinates was synthesized under high-pressure (25-54 GPa) high-temperature (2000-3000 K) conditions in laser-heated diamond anvil cells. The crystal structure of this novel class of compounds was determined via synchrotron single-crystal X-ray diffraction (SCXRD) as well as corroborated by X-ray absorption near edge structure (XANES) measurements and density functional theory (DFT) calculations. The Ln O (CN ) solids are composed of the hitherto unknown CN guanidinate anion-deprotonated guanidine.

Towards frustration in Eu(II) Archimedean tessellations.

Self-assembly of -{EuI} nodes and ditopic ligands leads to isoreticular 2D frameworks featuring a rare, non-kagome Archimedean tessellation. The topology and intra-layer Eu(II)-Eu(II) antiferromagnetic interactions provide the prerequisites for geometrical spin frustration, which, due to the spin state degeneracy, is key for novel phenomena such as enhanced magnetic refrigeration.

Metal-to-metal electron transfer in a cyanido-bridged {FeCo} square complex followed by X-ray diffraction and absorption techniques.

The switching properties of a cyanido-bridged Fe/Co square molecule were investigated by single-crystal X-ray diffraction and X-ray absorption spectroscopy at both Fe and Co K-edges. Combining these two techniques, a complete picture of the thermal-, light- and X-ray-induced metal-to-metal electron transfer is obtained, illustrating the concerted role played by the Fe and Co sites.

Comparative Study on the Magnetic and Transport Properties of B-Site Ordered and Disordered CaCuFeOsO.

The B-site Fe/Os ordered and disordered quadruple perovskite oxides CaCuFeOsO were synthesized under different high-pressure and high-temperature conditions. The B-site ordered CaCuFeOsO is a system with a very high ferrimagnetic ordering temperature of 580 K having the Cu(↑)Fe(↑)Os(↓) charge and spin arrangement. In comparison, the highly disordered CaCuFeOsO has a reduced magnetic transition temperature of about 350 K.

From an antiferromagnetic insulator to a strongly correlated metal in square-lattice MCl(pyrazine) coordination solids.

Electronic synergy between metal ions and organic linkers is a key to engineering molecule-based materials with a high electrical conductivity and, ultimately, metallicity. To enhance conductivity in metal-organic solids, chemists aim to bring the electrochemical potentials of the constituent metal ions and bridging organic ligands closer in a quest to obtain metal-d and ligand-π admixed frontier bands. Herein, we demonstrate the critical role of the metal ion in tuning the electronic ground state of such materials.

Origin of the Unusual Ground-State Spin = 9 in a Cr Single-Molecule Magnet.

The molecular wheel [Cr(OMe)(OCCMe)], abbreviated {Cr}, with an unusual intermediate total spin = 9 and non-negligible cluster anisotropy, / = -0.045(2) K, is a rare case among wheels based on an even number of 3d-metals, which usually present an antiferromagnetic (AF) ground state ( = 0). Herein, we unveil the origin of such a behavior.

XMCD and study of interface-engineered ultrathin Ru/Co/W/Ru films with perpendicular magnetic anisotropy and strong Dzyaloshinskii-Moriya interaction.

Understanding the nature of recently discovered spin-orbital induced phenomena and a definition of a general approach for "ferromagnet/heavy-metal" layered systems to enhance and manipulate spin-orbit coupling, spin-orbit torque, and the Dzyaloshinskii-Moriya interaction (DMI) assisted by atomic-scale interface engineering are essential for developing spintronics and spin-orbitronics. Here, we exploit X-ray magnetic circular dichroism (XMCD) spectroscopy at the -edges of 5d and 4d non-magnetic heavy metals (W and Ru, respectively) in ultrathin Ru/Co/W/Ru films to determine their induced magnetic moments due to the proximity to the ferromagnetic layer of Co. The deduced orbital and spin magnetic moments agree well with the theoretically predicted values, highlighting the drastic effect of constituting layers on the system's magnetic properties and the strong interfacial DMI in Ru/Co/W/Ru films.

Synthesis of Ilmenite-type ε-MnO and Its Properties.

In contrast to the corundum-type AX structure, which has only one crystallographic site available for trivalent cations (e.g., in hematite), the closely related ABX ilmenite-type structure comprises two different octahedrally coordinated positions that are usually filled with differently charged ions (e.

Hard X-ray magnetochiral dichroism in a paramagnetic molecular 4f complex.

Magnetochiral dichroism (MΧD) originates in the coupling of local electric fields and magnetic moments in systems where a simultaneous break of space parity and time-reversal symmetries occurs. This magnetoelectric coupling, displayed by chiral magnetic materials, can be exploited to manipulate the magnetic moment of molecular materials at the single molecule level. We demonstrate herein the first experimental observation of X-ray magnetochiral dichroism in enantiopure chiral trigonal single crystals of a chiral mononuclear paramagnetic lanthanide coordination complex, namely, holmium oxydiacetate, at the Ho L-edge.

Metal-organic magnets with large coercivity and ordering temperatures up to 242°C.

Magnets derived from inorganic materials (e.g., oxides, rare-earth-based, and intermetallic compounds) are key components of modern technological applications.

Rapid Discrimination of Crystal Handedness by X-ray Natural Circular Dichroism (XNCD) Mapping.

An original method for determining the handedness of individual non-centrosymmetric crystals in a mixture using a tightly-focused, circularly polarized X-ray beam is presented. The X-ray natural circular dichroism (XNCD) spectra recorded at the metal K-edge on selected crystals of [Δ-M(en) ](NO ) and [Λ-M(en) ](NO ) (M=Co , Ni ) show extrema at the metal pre-edge (7712 eV for Co, 8335 eV for Ni). A mapping of a collection of some 220 crystals was performed at the respective energies by using left and right circular polarizations.

A heteroleptic diradical Cr(iii) complex with extended spin delocalization and large intramolecular magnetic exchange.

Successive chemical reductions of the heteroleptic complex [(tpy)Cr(tphz)] (tpy = terpyridine; tphz = tetrapyridophenazine) give rise to the mono- and di-radical redox isomers, [(tpy)Cr(tphz˙)] and [(tpy˙)Cr(tphz˙)], respectively. As designed, the optimized overlap of the involved magnetic orbitals leads to extremely strong magnetic interactions between the S = 3/2 metal ion and S = 1/2 radical spins, affording well isolated S = 1 and S = 1/2 ground states at room temperature.

Access to Heteroleptic Fluorido-Cyanido Complexes with a Large Magnetic Anisotropy by Fluoride Abstraction.

Silicon-mediated fluoride abstraction is demonstrated as a means of generating the first fluorido-cyanido transition metal complexes. This new synthetic approach is exemplified by the synthesis and characterization of the heteroleptic complexes, trans-[M F (CN) ] (M=Re, Os), obtained from their homoleptic [M F ] parents. As shown by combined high-field electron paramagnetic resonance spectroscopy and magnetization measurements, the partial substitution of fluoride by cyanide ligands leads to a marked increase in the magnetic anisotropy of trans-[ReF (CN) ] as compared to [ReF ] , reflecting the severe departure from an ideal octahedral (O point group) ligand field.

[UF ] : A Molecular Hexafluorido Actinide(IV) Complex with Compensating Spin and Orbital Magnetic Moments.

The first structurally characterized hexafluorido complex of a tetravalent actinide ion, the [UF ] anion, is reported in the (NEt ) [UF ]⋅2 H O salt (1). The weak magnetic response of 1 results from both U spin and orbital contributions, as established by combining X-ray magnetic circular dichroism (XMCD) spectroscopy and bulk magnetization measurements. The spin and orbital moments are virtually identical in magnitude, but opposite in sign, resulting in an almost perfect cancellation, which is corroborated by ab initio calculations.

Using Redox-Active π Bridging Ligand as a Control Switch of Intramolecular Magnetic Interactions.

Intramolecular magnetic interactions in the dinuclear complexes [(tpy)Ni(tphz)Ni(tpy)] ( n = 4, 3, and 2; tpy, terpyridine; tphz, tetrapyridophenazine) were tailored by changing the oxidation state of the pyrazine-based bridging ligand. While its neutral form mediates a weak antiferromagnetic (AF) coupling between the two S = 1 Ni(II), its reduced form, tphz, promotes a remarkably large ferromagnetic exchange of +214(5) K with Ni(II) spins. Reducing twice the bridging ligand affords weak Ni-Ni interactions, in marked contrast to the Co(II) analogue.

Molecular multifunctionality preservation upon surface deposition for a chiral single-molecule magnet.

The synthesis and characterization of a chiral, enneanuclear Mn(iii)-based, Single-Molecule Magnet, [MnO(Me-sao)(L)(MeO)(MeOH)]Cl (; Me-saoH = methylsalicylaldoxime, HL = lipoic acid) is reported. Compound crystallizes in the orthorhombic 222 space group and consists of a metallic skeleton describing a defect super-tetrahedron missing one vertex. The chirality of the [Mn ] core originates from the directional bridging of the Me-sao ligands the -N-O- oximate moieties, which define a clockwise () or counter-clockwise () rotation in both the upper [Mn ] and lower [Mn ] subunits.

Integration of LaMnO films on platinized silicon substrates for resistive switching applications by PI-MOCVD.

The next generation of electronic devices requires faster operation velocity, higher storage capacity and reduction of the power consumption. In this context, resistive switching memory chips emerge as promising candidates for developing new non-volatile memory modules. Manganites have received increasing interest as memristive material as they exhibit a remarkable switching response.

Revisiting Bond Breaking and Making in EuCo P : Where are the Electrons?

X-ray absorption spectroscopy (XAS) was used to elucidate changes in the electronic structure caused by the pressure-induced structural collapse in EuCo P . The spectral changes observed at the L -edge of Eu and K-edges of Co and P suggest electron density redistribution, which contradicts the formal charges calculated from the commonly used Zintl-Klemm concept. Quantum-chemical calculations show that, despite the increase in the oxidation state of Eu and the formation of a weak P-P bond in the high-pressure phase, the electron transfer from the Eu 4f orbitals to the hybridized 5d and 6s states causes strengthening of the Eu-P and P-P bonds.

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.

Formation of the layered conductive magnet CrCl(pyrazine) through redox-active coordination chemistry.

The unique properties of graphene, transition-metal dichalcogenides and other two-dimensional (2D) materials have boosted interest in layered coordination solids. In particular, 2D materials that behave as both conductors and magnets could find applications in quantum magnetoelectronics and spintronics. Here, we report the synthesis of CrCl(pyrazine), an air-stable layered solid, by reaction of CrCl with pyrazine (pyz).

XMCD studies of magnetic polarization at Mo atoms in CoMo alloy and magnetically coupled Co/Mo multilayers.

Magnetic polarization of Mo atoms in CoMo alloy film and Co/Mo multilayered structures has been studied by X-ray magnetic circular dichroism. Samples with Mo spacers of two different thicknesses (0.9 nm and 1.