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.

Magnon thermal Hall effect via emergent SU(3) flux on the antiferromagnetic skyrmion lattice.

Complexity of quantum phases of matter is often understood theoretically by using gauge structures, as is recognized by the [Formula: see text] and U(1) gauge theory description of spin liquids in frustrated magnets. Anomalous Hall effect of conducting electrons can intrinsically arise from a U(1) gauge expressing the spatial modulation of ferromagnetic moments or from an SU(2) gauge representing the spin-orbit coupling effect. Similarly, in insulating ferro and antiferromagnets, the magnon contribution to anomalous transports is explained in terms of U(1) and SU(2) fluxes present in the ordered magnetic structure. Here, we report thermal Hall measurements of MnSc2S4 in an applied field up to 14 T, for which we consider an emergent higher rank SU(3) flux, controlling the magnon transport. The thermal Hall coefficient takes a substantial value when the material enters a three-sublattice antiferromagnetic skyrmion phase, which is in agreement with the linear spin-wave theory. In our description, magnons are dressed with SU(3) gauge field, which is a mixture of three species of U(1) gauge fields originating from the slowly varying magnetic moments on these sublattices.

X-ray magnetic circular dichroism investigation of the electron transfer phenomena responsible for magnetic switching in a cyanide-bridged [CoFe] chain.

The cyanide-bridged [CoFe] one-dimensional chain, [Co(II)((R)-pabn)][Fe(III)(Tp)(CN)3](BF4)·MeOH·2H2O, where (R)-pabn = (R)-N2,N(2')-bis(pyridin-2-ylmethyl)-1,1'-binaphthyl-2,2'-diamine and Tp = hydrotris(pyrazolyl)borate, exhibits magnetic and electric bistabilities originating from an electron transfer coupled spin transition between Fe-CN-Co pairs. The use of L-edge X-ray absorption spectroscopy (XAS) in combination with L-edge X-ray magnetic circular dichroism (XMCD) is explored for the investigation of the electronic structure and magnetization of Co and Fe ions separately, in both diamagnetic and paramagnetic states. It has been established from susceptibility results that the switching between diamagnetic and paramagnetic phases emanates from electron transfer between low spin Fe(II) and Co(III), resulting in low spin Fe(III) (S = 1/2) and high spin Co(II) (S = 3/2). The XAS and XMCD results are consistent with the bulk susceptibility measurements, where greater detail regarding the charge transfer process is determined. The Fe-CN-Co electron transfer pathway is highlighted by a strongly XMCD dependent transition to a cyanide back bonding orbital, giving evidence for strong hybridization with Fe(III) t2g orbitals. In addition to thermally induced and photoinduced switching, [CoFe] is found to exhibit a switching by grinding induced dehydration. Analysis of XAS shows that on grinding diamagnetic [CoFe], 75% of metal ions lock into the magnetic Co(II)Fe(III) phase. Density functional theory calculations based on the [CoFe] crystal structure in the magnetic and nonmagnetic phases aid the spectroscopic results and provide a complementary insight into the electronic configuration of the [CoFe] 3d shells, quantifying the change in ligand field around Co and Fe centers on charge transfer.

Piston-cylinder cell made of Ni-Cr-Al alloy for magnetic susceptibility measurements under high pressures in pulsed high magnetic fields.

We developed a metallic pressure cell made of 56Ni-40Cr-4Al (Ni-Cr-Al) alloy for use with a non-destructive pulse magnet and a magnetic susceptibility measurement apparatus with a proximity detector oscillator (PDO) in pulsed magnetic fields of up to 51 T under pressures of up to 2.1 GPa. Both the sample and sensor coil of the PDO were placed in the cell so that the magnetic signal from Ni-Cr-Al would not overlay the intrinsic magnetic susceptibility of the sample. A systematic investigation of the Joule heating originating from metallic parts of the pressure cell revealed that the increase in sample temperature is negligible at 1.4 K in magnetic fields of up to 40 T in the field-ascending process for the maximum applied magnetic field of 51 T. The effectiveness of our apparatus was demonstrated by investigating the pressure dependence of the magnetization process of the triangular-lattice antiferromagnet Ba3CoSb2O9.

The Forced Magnetostrictions and Magnetic Properties of Ni2MnX (X = In, Sn) Ferromagnetic Heusler Alloys.

Experimental studies into the forced magnetostriction, magnetization, and temperature dependence of permeability in Ni2MnIn and Ni2MnSn ferromagnetic Heusler alloys were performed according to the spin fluctuation theory of itinerant ferromagnetism proposed by Takahashi. We investigated the magnetic field (H) dependence of magnetization (M) at the Curie temperature TC, and at T = 4.2 K, which concerns the ground state of the ferromagnetic state. The M-H result at TC was analyzed by means of the H versus M5 dependence. At 4.2 K, it was investigated by means of an Arrott plot (H/M vs. M2) according to Takahashi's theory. As for Ni2MnIn and Ni2MnSn, the spin fluctuation parameters in k-space (momentum space, TA) and that in energy space (frequency space, T0) obtained at TC and 4.2 K were almost the same. The average values obtained at TC and 4.2 K were TA = 342 K, T0 = 276 K for Ni2MnIn and TA = 447 K, T0 = 279 K for Ni2MnSn, respectively. The forced magnetostriction at TC was also investigated. The forced linear magnetostriction (ΔL/L) and the forced volume magnetostriction (ΔV/V) were proportional to M4, which followed Takahashi's theory. We compared the forced volume magnetostriction ΔV/V and mechanical parameter, bulk modulus K. ΔV/V is inversely proportional to K. We also discuss the spin polarization of Ni2MnIn and other magnetic Heusler alloys. The pC/pS of Ni2MnIn was 0.860. This is comparable with that of Co2MnGa, which is a famous half-metallic alloy.

Forced Magnetostrictions and Magnetizations of Ni2+xMnGa1-x at Its Curie Temperature.

Experimental investigations into the field dependence of magnetization and the relationship between magnetization and magnetostriction in Ni2+xMnGa1-x (x = 0.00, 0.02, 0.04) alloy ferromagnets were performed following the self-consistent renormalization (SCR) spin fluctuation theory of itinerant ferromagnetism. In this study, we investigated the magnetization of and magnetostriction on Ni2+xMnGa1-x (x = 0.02, 0.04) to check whether these relations held when the ratio of Ni to Ga and, the valence electron concentration per atom, e/a were varied. When the ratio of Ni to Ga was varied, e/a increased with increasing x. The magnetization results for x = 0.02 (e/a = 7.535) and 0.04 (e/a = 7.570) suggest that the critical index δ of H ∝ Mδ is around 5.0 at the Curie temperature TC, which is the critical temperature of the ferromagnetic⁻paramagnetic transition. This result confirms Takahashi's spin fluctuation theory and the experimental results of Ni2MnGa. The spontaneous magnetization pS slightly decreased with increasing x. For x = 0.00, the spin fluctuation parameter in k-space (momentum space; TA) and that in energy space (T0) were obtained. The relationship between peff/pS and TC/T0 can also be explained by Takahashi's theory, where peff indicates the effective magnetic moments. We created a generalized Rhodes-Wohlfarth plot of peff/pS versus TC/T0 for other ferromagnets. The plot indicates that the relationship between peff/pS and T0/TC follows Takahashi's theory. We also measured the magnetostriction for Ni2+xMnGa1-x (x = 0.02, 0.04). As a result, at TC, the plot of the magnetostriction (ΔL/L) versus M4 shows proportionality and crosses the origin. These magnetization and magnetostriction results were analyzed in terms of Takahashi's SCR spin fluctuation theory. We investigated the magnetostriction at the premartensite phase, which is the precursor state to the martensitic transition. In Ni2MnGa system alloys, the maximum value of magnetostriction is almost proportional to the e/a.

Synthesis and magnetic properties of a new series of triangular-lattice magnets, Na2BaMV2O8 (M = Ni, Co, and Mn).

A new series of triangular-lattice magnets, Na(2)BaMV(2)O(8) (M = Ni, Co, and Mn), are reported. These three compounds crystallize with the Ag(2)BaMnV(2)O(8) type structure, where the magnetic M(2+) ions form a two-dimensional triangular lattice. The magnitude of the exchange interactions in these compounds is moderate because the nonmagnetic VO(4) tetrahedra interrupt direct connections between MO(6) octahedra. The magnetic susceptibilities of Na(2)BaNiV(2)O(8) and Na(2)BaCoV(2)O(8) reveal ferromagnetic transitions at 8.4 and 3.9 K, respectively. In contrast, the magnetic susceptibility of Na(2)BaMnV(2)O(8) exhibits a broad maximum at around 2.3 K, which suggests antiferromagnetic nearest-neighbour interactions and a significant effect of geometric frustration. The specific heat and magnetization curve of Na(2)BaMnV(2)O(8) indicate that magnetic long-range ordering appears below 1.5 K.

A single-solenoid pulsed-magnet system for single-crystal scattering studies.

We present a pulsed-magnet system that enables x-ray single-crystal diffraction in addition to powder and spectroscopic studies with the magnetic field applied on or close to the scattering plane. The apparatus consists of a single large-bore solenoid, cooled by liquid nitrogen. A second independent closed-cycle cryostat is used for cooling samples near liquid helium temperatures. Pulsed magnetic fields close to ~30 T with a zero-to-peak-field rise time of ~2.9 ms are generated by discharging a 40 kJ capacitor bank into the magnet coil. The unique characteristic of this instrument is the preservation of maximum scattering angle (~23.6°) on the entrance and exit sides of the magnet bore by virtue of a novel double-funnel insert. This instrument will facilitate x-ray diffraction and spectroscopic studies that are impractical, if not impossible, to perform using split-pair and narrow-opening solenoid magnets. Furthermore, it offers a practical solution for preserving optical access in future higher-field pulsed magnets.

Module-based assembly of copper(II) chloranilate compounds: syntheses, crystal structures, and magnetic properties of [[Cu(2)(CA)(terpy)(2)][Cu(CA)(2)]](n)() and [[Cu(2)(CA)(terpy)(2)(dmso)(2)][Cu(CA)(2)(dmso)(2)](EtOH)](n)(H(2)CA = chloranilic acid, terpy = 2,2':6',2' '-terpyridine, dmso = dimethyl sulfoxide).

Two new copper(II) compounds of chloranilate and 2,2':6',2' '-terpyridine have been synthesized, and the structures have been solved by the single-crystal X-ray diffraction method. The crystal structure of [[Cu(2)(CA)(terpy)(2)][Cu(CA)(2)]](n)(1), where H(2)CA = chloranilic acid and terpy = 2,2':6',2' '-terpyridine, consists of two modules, the dimer unit [Cu(2)(CA)(terpy)(2)](2+) and the anionic mononuclear unit [Cu(CA)(2)](2)(-), forming an alternated chain. The chain is stabilized by semicoordinating and additional but efficient secondary bonding interactions. The crystal structure of [[Cu(2)(CA)(terpy)(2)(dmso)(2)][Cu(CA)(2)(dmso)(2)](EtOH)](n)(2), where dmso = dimethyl sulfoxide, consists of solvent molecules and two discrete modules, the dimer unit [Cu(2)(CA)(terpy)(2)(dmso)(2)](2+) and the anionic mononuclear unit [Cu(CA)(2)(dmso)(2)](2)(-). The dimer units form a layer by secondary bonding interactions, and the monomer units and ethanol molecules are introduced between the layers. The magnetic properties of 1 and 2 have been investigated in the temperature range 2.0-300 K. A weak ferromagnetic interaction was observed in 1, J(a) = 2.36 cm(-)(1) and zJ(b) = -0.68 cm(-)(1) while no exchange coupling was observed in 2.