A correlated ferromagnetic polar metal by design.

Polar metals have recently garnered increasing interest because of their promising functionalities. Here we report the experimental realization of an intrinsic coexisting ferromagnetism, polar distortion and metallicity in quasi-two-dimensional Ca3Co3O8. This material crystallizes with alternating stacking of oxygen tetrahedral CoO4 monolayers and octahedral CoO6 bilayers. The ferromagnetic metallic state is confined within the quasi-two-dimensional CoO6 layers, and the broken inversion symmetry arises simultaneously from the Co displacements. The breaking of both spatial-inversion and time-reversal symmetries, along with their strong coupling, gives rise to an intrinsic magnetochiral anisotropy with exotic magnetic field-free non-reciprocal electrical resistivity. An extraordinarily robust topological Hall effect persists over a broad temperature-magnetic field phase space, arising from dipole-induced Rashba spin-orbit coupling. Our work not only provides a rich platform to explore the coupling between polarity and magnetism in a metallic system, with extensive potential applications, but also defines a novel design strategy to access exotic correlated electronic states.

Investigation of the impact of A-site cation disorder on the structure, magnetic properties, and magnetic entropy change of trisubstituted divalent ions in La0.7(Ba,Ca,Sr)0.3MnO3 manganite.

This study investigates the effect of A-site disorder, characterized by the average ionic radius (〈rA〉) and the cation mismatch (σ2), on the structural, magnetic, critical behavior, and magnetic entropy changes in La0.7(Ba,Ca,Sr)0.3MnO3 manganites with trisubstituted Ba, Ca, and Sr. The sol-gel method was used to prepare polycrystalline samples. All series of compounds crystallize in rhombohedral symmetry with the R3̄c space group. A linear relationship between lattice parameters, unit cell volume, and 〈rA〉 was observed. This reveals an unusual behavior in the correlation between 〈rA〉 and σ2 concerning magnetic properties, which is attributed to the complex simultaneous trisubstitution of divalent ions. Energy dispersive spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS) were utilized to validate the chemical composition of compounds. All the samples crystallized in rhombohedral symmetry, and the lattice parameters increased continuously with increasing 〈rA〉. A-site disorder causes distortions in the Mn-O bond length and Mn-O-Mn bond angle in the MnO6 octahedral structure, which influences the double-exchange interaction and electronic bandwidth (W). The Curie temperature (TC) increases linearly with increasing W. The critical behavior around TC for all the samples was investigated by determining the values of the critical exponents (ß, γ, and δ) using the modified Arrott plot (MAP) method. The estimated critical exponents show that the unconventional model establishes a short-range ferromagnetic order. The maximum magnetic entropy change (-ΔSM) was obtained with the lowest 〈rA〉 and σ2 value. The analysis of the critical behavior and universal curve indicates a second-order phase transition (SOPT) nature for all samples.

Stellated cuboctahedron of FeIII.

The solvothermal reaction of FeCl2·4H2O and H4TBC[4] in a basic dmf/EtOH solution affords an [FeIII18] Keplerate conforming to a stellated cuboctahedron. Magnetic measurements reveal spin frustration effects arising from the high symmetry.

Zero-Field SMM Behavior Triggered by Magnetic Exchange Interactions and a Collinear Arrangement of Local Anisotropy Axes in a Linear Co3II Complex.

A new linear trinuclear Co(II)3 complex with a formula of [{Co(µ-L)}2Co] has been prepared by self-assembly of Co(II) ions and the N3O3-tripodal Schiff base ligand H3L, which is obtained from the condensation of 1,1,1-tris(aminomethyl)ethane and salicylaldehyde. Single X-ray diffraction shows that this compound is centrosymmetric with triple-phenolate bridging groups connecting neighboring Co(II) ions, leading to a paddle-wheel-like structure with a pseudo-C3 axis lying in the Co-Co-Co direction. The Co(II) ions at both ends of the Co(II)3 molecule exhibit distorted trigonal prismatic CoN3O3 geometry, whereas the Co(II) at the middle presents an elongated trigonal antiprismatic CoO6 geometry. The combined analysis of the magnetic data and theoretical calculations reveal strong easy-axis magnetic anisotropy for both types of Co(II) ions (|D| values higher than 115 cm-1) with the local anisotropic axes lying on the pseudo-C3 axis of the molecule. The magnetic exchange interaction between the middle and ends Co(II) ions, extracted by using either a Hamiltonian accounting for the isotropic magnetic coupling and ZFS or the Lines' model, was found to be medium to strong and antiferromagnetic in nature, whereas the interaction between the external Co(II) ions is weak antiferromagnetic. Interestingly, the compound exhibits slow relaxation of magnetization and open hysteresis at zero field and therefore SMM behavior. The significant magnetic exchange coupling found for [{Co(µ-L)}2Co] is mainly responsible for the quenching of QTM, which combined with the easy-axis local anisotropy of the CoII ions and the collinearity of their local anisotropy axes with the pseudo-C3 axis favors the observation of SMM behavior at zero field.

{ScnGdn} Heterometallic Rings: Tunable Ring Topology for Spin-Wave Excitations.

Data carriers using spin waves in spintronic and magnonic logic devices offer operation at low power consumption and free of Joule heating yet requiring noncollinear spin structures of small sizes. Heterometallic rings can provide such an opportunity due to the controlled spin-wave transmission within such a confined space. Here, we present a series of {ScnGdn} (n = 4, 6, 8) heterometallic rings, which are the first Sc-Ln clusters to date, with tunable magnetic interactions for spin-wave excitations. By means of time- and temperature-dependent spin dynamics simulations, we are able to predict distinct spin-wave excitations at finite temperatures for Sc4Gd4, Sc6Gd6, and Sc8Gd8. Such a new model is previously unexploited, especially due to the interplay of antiferromagnetic exchange, dipole-dipole interaction, and ring topology at low temperatures, rendering the importance of the latter to spin-wave excitations.

Magnetic Control of Soft Chiral Phonons in PbTe.

PbTe crystals have a soft transverse optical phonon mode in the terahertz frequency range, which is known to efficiently decay into heat-carrying acoustic phonons, resulting in anomalously low thermal conductivity. Here, we studied this phonon via polarization-dependent terahertz spectroscopy. We observed softening of this mode with decreasing temperature, indicative of incipient ferroelectricity, which we explain through a model including strong anharmonicity with a quartic displacement term. In magnetic fields up to 25 T, the phonon mode splits into two modes with opposite handedness, exhibiting circular dichroism. Their frequencies display Zeeman splitting together with an overall diamagnetic shift with increasing magnetic field. Using a group-theoretical approach, we demonstrate that these observations are the result of magnetic field-induced morphic changes in the crystal symmetries through the Lorentz force exerted on the lattice ions. Thus, our Letter reveals a novel process of controlling phonon properties in a soft ionic lattice by a strong magnetic field.

A Ferromagnetically Coupled Octanuclear Manganese(III) Cluster: A Single-Molecule Magnet with a Spin Ground State of S = 16.

An octanuclear manganese complex, [MnIII8(µ4-O)4(L)4(OMe)4(OAc)4(OCH2CH2NH3)4] [1; H2L = 3-(dimethoxymethyl)-2-hydroxybenzoic acid], was synthesized with an extended cubane core structure consisting of eight Mn ions bridged by O atoms. Cryomagnetic studies revealed that 1 showed a single-molecule-magnet behavior with an S = 16 spin ground state.

Triplet Diradical-Cation Salts Consisting of the Phenothiazine Radical Cation and a Nitronyl Nitroxide.

The spin-spin and magnetic properties of two (nitronyl nitroxide)-(di-p-anisylamine-phenothiazine) diradical cation salts, (DAA-PTZ)+ -NN⋅MBr4 - (M=Ga, Fe), have been investigated. These diradical-cation species were prepared by the cross-coupling of iodophenothiazine DAA-PTZ-I with NN-AuPPh3 followed by oxidation with the thianthrenium radical cation (TA+ ⋅MBr4 - ). These salts were found to be highly stable under aerobic conditions. For the GaBr4 salt, large ferromagnetic intramolecular and small antiferromagnetic intermolecular interactions (J1 /kB =+320 K and J2 /kB =-2 K, respectively) were observed. The magnetic property of the Fe3+ salt was analyzed by using a six-spin model assuming identical intramolecular exchange interaction (J3 /kB =+320 K) and the other exchange interactions (J4 /kB =-7 K and J5 /kB =-4 K). A significant color change was observed in the UV/Vis/NIR absorption spectra upon electrochemical oxidation of the doublet DAA-PTZ-NN to the triplet (DAA-PTZ)+ -NN.

Electron-Transfer Activity in a Cyanide-Bridged Fe42 Nanomagnet.

The ability to switch a molecule between different magnetic states is of considerable importance for the development of new molecular electronic devices. Desirable properties for such applications include a large-spin ground state with an electronic structure that can be controlled via external stimuli. Fe42 is a cyanide-bridged stellated cuboctahedron of mixed-valence Fe ions that exhibits an extraordinarily large S = 45 spin ground state. We have found that the spin ground state of Fe42 can be altered by controlling the humidity and temperature. Dehydration results in a 15 µB reduction of the saturation magnetization that can be partially recovered upon rehydration. The complementary use of UV-vis, IR, L2,3-edge X-ray absorption spectroscopy and X-ray magnetic circular dichroism is applied to uncover the mechanism for the observed dynamic behavior. It is identified that dehydration is concurrent with metal-to-metal electron transfer between Fe pairs via a cyanide π hybridization. Upon dehydration, electron transfer occurs from low-spin {FeII(Tp)(CN)3} sites to high-spin FeIII centers. The observed reduction in magnetization upon dehydration of Fe42 is inconsistent with a ferrimagnetic ground state and is proposed to originate from a change in zero-field splitting at electron-reduced high-spin sites.

An [FeIII 34 ] Molecular Metal Oxide.

The dissolution of anhydrous iron bromide in a mixture of pyridine and acetonitrile, in the presence of an organic amine, results in the formation of an [Fe34 ] metal oxide molecule, structurally characterised by alternate layers of tetrahedral and octahedral FeIII ions connected by oxide and hydroxide ions. The outer shell of the complex is capped by a combination of pyridine molecules and bromide ions. Magnetic data, measured at temperatures as low as 0.4 K and fields up to 35 T, reveal competing antiferromagnetic exchange interactions; DFT calculations showing that the magnitudes of the coupling constants are highly dependent on both the Fe-O-Fe angles and Fe-O distances. The simplicity of the synthetic methodology, and the structural similarity between [Fe34 ], bulk iron oxides, previous FeIII -oxo cages, and polyoxometalates (POMs), hints that much larger molecular FeIII oxides can be made.

Slow Magnetic Relaxation in a Palladium-Gadolinium Complex Induced by Electron Density Donation from the Palladium Ion.

Incorporating palladium in the first coordination sphere of acetato-bridged lanthanoid complexes, [Pd2 Ln2 (H2 O)2 (AcO)10 ]⋅2 AcOH (Ln=Gd (1), Y (2), Gd0.4 Y1.6 (3), Eu (4)), led to significant bonding interactions between the palladium and the lanthanoid ions, which were demonstrated by experimental and theoretical methods. We found that electron density was donated from the d8 Pd2+ ion to Gd3+ ion in 1 and 3, leading to the observed slow magnetic relaxation by using local orbital locator (LOL) and X-ray absorption near-edge structure (XANES) analysis. Field-induced dual slow magnetic relaxation was observed for 1 up to 20 K. Complex 3 and frozen aqueous and acetonitrile solutions of 1 showed only one relaxation peak, which confirms the role of intermolecular dipolar interactions in slowing the magnetic relaxation of 1. The slow magnetic relaxation occurred through a combination of Orbach and Direct processes with the highest pre-exponential factor (τo =0.06 s) reported so far for a gadolinium complex exhibiting slow magnetic relaxation. The results revealed that transition metal-lanthanoid (TM-Ln) axial interactions indeed could lead to new physical properties by affecting both the electronic and magnetic states of the compounds.

Topological Self-Assembly of Highly Symmetric Lanthanide Clusters: A Magnetic Study of Exchange-Coupling "Fingerprints" in Giant Gadolinium(III) Cages.

The creation of a perfect hollow nanoscopic sphere of metal centers is clearly an unrealizable synthetic challenge. It is, however, an inspirational challenge from the viewpoint of chemical architecture and also as finite molecular species may provide unique microscopic insight into the origin and onset of phenomena such as topological spin-frustration effects found in infinite 2D and 3D systems. Herein, we report a series of high-symmetry gadolinium(III) (S = 7/2) polyhedra, Gd20, Gd32, Gd50, and Gd60, to test an approach based on assembling polymetallic fragments that contain different polygons. Structural analysis reveals that the Gd20 cage resembles a dodecahedron; the vertices of the Gd32 polyhedron exactly reveal symmetry Oh; Gd50 displays an unprecedented polyhedron in which an icosidodecahedron Gd30 core is encapsulated by an outer Gd20 dodecahedral shell with approximate Ih symmetry; and the Gd60 shows a truncated octahedron geometry. Experimental and theoretical magnetic studies show that this series produces the expected antiferromagnetic interaction that can be modeled based on classical spins at the Gd sites. From the magnetization analyses, we can roughly correlate the derivative bands to the Gd-O-Gd angles. Such a magneto-structural correlation may be used as "fingerprints" to identify these cages.

Field-Induced Slow Magnetic Relaxation of GdIII Complex with a Pt-Gd Heterometallic Bond.

Heterometallic Gd-Pt complexes ([Gd2 Pt3 (H2 O)2 (SAc)12 ] (SAc=thioacetate), [Y1.4 Gd0.6 Pt3 (H2 O)2 (SAc)12 ], and [Gd2 Pt3 (H2 O)6 (SAc)12 ]⋅7 H2 O have been synthesized. The crystal structures and DFT calculations indicated a Gd-Pt heretometallic bond. Single-crystal ESR spectra determined the direction of magnetic anisotropy as direction of the Gd-Pt bond. In other words, the Gd-Pt bond dictates the direction of magnetic anisotropy. The heterometallic Gd-Pt bond lowers the symmetry of the Gd ion, splitting the Kramers doublet in a dc field. Thus, we observed clear field-induced slow magnetic relaxation of [Y1.4 Gd0.6 Pt3 (H2 O)2 (SAc)12 ] up to 36 K. The relaxation process was determined to be a direct process.

Design of a Family of Ln3 Triangles with the HAT Ligand (1,4,5,8,9,12-Hexaazatriphenylene): Single-Molecule Magnetism.

A series of trinuclear Ln3 complexes (LnIII = Yb (1), Er (2), Dy (3) and Gd (4)) were prepared from the tris-chelate bidentate ligand 1,4,5,8,9,12-hexaazatriphenylene (HAT). 1 and 2 exhibited field-induced single-molecule-magnet (SMM) behavior with estimated Ueff values of 21.30 and 13.86 K, respectively. Complex 3 behaved as a SMM even at zero field, and two different thermally assisted relaxation processes were detected with Ueff values of 29.6 K (fast relaxation process, FR) and 69 K (slow relaxation process, SR) due to the existence of two magnetically different DyIII centers in the molecule. Ab initio studies reveal that all the Dy3+ centers have almost an Ising ground state. The local anisotropy axes are not coplanar but form angles with the Dy3 plane in the range 58-78°. The magnetic interaction between the anisotropic Dy3+ ions is antiferromagnetic in nature and very weak in magnitude. However, due to the extreme feebleness of the magnetic interaction with regard to the local excitation energies, the magnetization blockade is most probably of single-ion origin. Calculations support the existence of two relaxation processes, which take place through the first excited state following an Orbach/Raman mechanism. Finally, for complex 4, the magnetocaloric effect was simulated using the magnetic parameters extracted from the fit of the magnetization and susceptibility data and demonstrated that the simulated -ΔSm values were almost coincident with those extracted from the integration of the field dependence of the magnetization. The simulated MCE value at 2 K and 5 T (20.46 J kg-1 K-1) makes complex 4 an attractive candidate for cryogenic magnetization.

Giant Exchange Coupling Evidenced with a Magnetization Jump at 52 T for a Gadolinium-Nitroxide Chelate.

The Gd-radical complex [GdIII(hfac)3(6bpyNO)] (6bpyNO = 2,2'-bipyridin-6-yl tert-butyl nitroxide; Hhfac = 1,1,1,5,5,5-hexafluoropentane-2,4-dione) showed a magnetization jump at 52 T observed in a pulsed-field facility, corresponding to an exchange coupling constant of -17.4 K. Furthermore, hysteretic behavior due to a relatively slow magnetization reversal was recorded around 2 T. From the high-frequency EPR study, the exchange coupling between Gd and radical spins accompanies an anisotropic character, which is responsible for both the broad jump and the slow magnetization reversal.

Quantum Monte Carlo Simulations and High-Field Magnetization Studies of Antiferromagnetic Interactions in a Giant Hetero-Spin Ring.

Chromium lanthanide heterometallic wheel complexes {Cr8 Ln8 } (Ln=Gd, Dy and Y) with alternating metal centres are presented. Quantum Monte Carlo simulations reveal antiferromagnetic exchange-coupling constants with an average of 2.1 K within the {Cr8 Gd8 } wheel, which leads to a large ground spin state (ST =16) that is confirmed by magnetization studies up to 20 Tesla. The {Cr8 Dy8 } wheel is a single-molecule magnet.

Anisotropic Change in the Magnetic Susceptibility of a Dynamic Single Crystal of a Cobalt(II) Complex.

Atypically anisotropic and large changes in magnetic susceptibility, along with a change in crystalline shape, were observed in a CoII complex at near room temperature. This was achieved by combining oxalate molecules, acting as rotor, and a CoII ion with unquenched orbital angular momentum. A thermally controlled 90° rotation of the oxalate counter anion triggered a symmetry-breaking ferroelastic phase transition, accompanied by contraction-expansion behavior (ca. 4.5 %) along the long axis of a rod-like single crystal. The molecular rotation induced a minute variation in the coordination geometry around the CoII ion, resulting in an abrupt decrease and a remarkable increase in magnetic susceptibility along the direction perpendicular and parallel to the long axis of the crystal, respectively. Theoretical calculations suggested that such an unusual anisotropic change in magnetic susceptibility was due to a substantial reorientation of magnetic anisotropy induced by slight disruption in the ideal D3 coordination environment of the complex cation.

Single-shot terahertz time-domain spectroscopy in pulsed high magnetic fields.

We have developed a single-shot terahertz time-domain spectrometer to perform optical-pump/terahertz-probe experiments in pulsed, high magnetic fields up to 30 T. The single-shot detection scheme for measuring a terahertz waveform incorporates a reflective echelon to create time-delayed beamlets across the intensity profile of the optical gate beam before it spatially and temporally overlaps with the terahertz radiation in a ZnTe detection crystal. After imaging the gate beam onto a camera, we can retrieve the terahertz time-domain waveform by analyzing the resulting image. To demonstrate the utility of our technique, we measured cyclotron resonance absorption of optically excited carriers in the terahertz frequency range in intrinsic silicon at high magnetic fields, with results that agree well with published values.

Studies on the Magnetic Ground State of a Spin Möbius Strip.

Here we report the synthesis, structure and detailed characterisation of three n-membered oxovanadium rings, Nan [(V=O)n Nan (H2 O)n (α, ß, or γ-CD)2 ]⋅m H2 O (n=6, 7, or 8), prepared by the reactions of (V=O)SO4 ⋅x H2 O with α, ß, or γ-cyclodextrins (CDs) and NaOH in water. Their alternating heterometallic vanadium/sodium cyclic core structures were sandwiched between two CD moieties such that O-Na-O groups separated the neighbouring vanadyl ions. Antiferromagnetic interactions between the S=1/2 vanadyl ions led to S=0 ground states for the even-membered rings, but to two quasi-degenerate S=1/2 states for the spin-frustrated heptanuclear cluster.

Copper Keplerates: High-Symmetry Magnetic Molecules.

Keplerates are molecules that contain metal polyhedra that describe both Platonic and Archimedean solids; new copper keplerates are reported, with physical studies indicating that even where very high molecular symmetry is found, the low-temperature physics does not necessarily reflect this symmetry.