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We have developed a pressure calibration method in the high-pressure THz ESR system using induction coils set outside the pressure cell. The pressure is calibrated using alternating current (AC) magnetization measurements of the superconducting transition temperature of tin set inside the pressure cell with an ESR sample. The system fits the developed pressure cell with a wide frequency range of 0.05–0.8 THz. The pressure range was extended to 2.8 GPa. The ESR system was applied to the well-known cobalt Tutton’s salt $$({\text {NH}}_{4})_{2} {\rm {Co}}({\text {SO}}_{4})_{2}\cdot {\rm {6H}}_{2} {\text {O}}$$ , and its g principal values at 0 GPa were determined as $$g_{1}=6.61$$ , $$g_{2}=3.05$$ , and $$g_{3}=2.94$$ for the first time. Furthermore, we succeeded in observing the large change in these g values with pressure.

In solid-state physics, pressure is an essential parameter, which can continuously change the interaction between electrons. The combination of terahertz electron spin resonance (THz ESR) with pressure is a powerful approach to clarify the spin state under pressure from the microscopic point of view, especially for quantum magnets. The most important feature of our high-pressure THz ESR system is that our pressure cell ensures the high pressure and wide frequency range using ceramics in internal parts, which are well balanced in terms of toughness and transmittance of electromagnetic waves. This approach allowed to very accurately describe the spin state under pressure. In this review, high-pressure ESR systems are reviewed with a focus on those in the high-frequency region. In addition, we show differences between other systems and our system. Moreover, we show the usefulness of our system by showing application examples of several magnetic materials of interest.

We systematically studied the zero-field splitting (ZFS) parameters of Fe(III) protoporphyrin IX chloride, or hemin, using the terahertz electron paramagnetic resonance (EPR) spectroscopy technique at ambient and high pressures. Although hemin is known as a model substance of hemoproteins, the pressure effect on the electronic structure has not yet been explored owing to the large ZFS. In this study, high-field and high-frequency EPR measurements were carried out in the frequency range up to 700 GHz and at hydrostatic pressures up to 2 GPa. At ambient pressure, multiple EPR branches were clearly observed, and the axial and rhombic components of ZFS were determined as $$D = 6.90\pm 0.01\hbox { cm}^{-1}$$ and $$E = 0.055 \pm 0.005\hbox { cm}^{-1}$$ , respectively. Upon pressure application, we observed a systematic shift of the resonance field, indicating a monotonous increase of the axial component from D = 6.9 to 7.9 $$\hbox {cm}^{-1}$$ at 2 GPa. The origin of this unusually large shift was discussed from a microscopic viewpoint of the electronic structure of iron under pressure.

Salts of cationic sandwich complexes often exhibit an ionic plastic phase; however, only a few exhibit a plastic phase at room temperature. To explore the use of the CF3BF3 anion to lower the transition temperature to the plastic phase, we prepared salts of CF3BF3 with various ferrocene derivatives, [D][CF3BF3] (D=FeCp*(2), Fe(C5Me4H)(2), Fe(C5H4Me)(2), FeCp(C5H4Me), FeCp2; Cp*=C5Me5, Cp=C5H5). Although [FeCp*(2)][CF3BF3] exhibited a plastic phase above 417 K, the other salts formed room-temperature ionic plastic crystals with a phase transition to the plastic phase in the range 266-291 K. The crystal structure and thermal properties of [FeCp2][OTf] were elucidated for comparison. In addition, decamethylferrocenium salts with other anions were synthesized and structurally characterized: [FeCp*(2)][X] (X=N(SO2F)(2) and B(CN)(4)) exhibited a phase transition to the plastic phase above 400 K, whereas carborane-containing salts [FeCp*(2)](2)[B12F12] and [FeCp*(2)][Co(C2B9H11)(2)] did not exhibit a plastic phase.

We synthesized paramagnetic organometallic ionic liquids [Fe(C5Me4Bu)(SC6H4R)(CO){P(OEt)3}][Tf2N] (R = CF3 (1), H (2), OMe (3)), comprising a cationic half-metallocenium iron-thiolate complex and a bis(trifluoromethanesulfonyl)amide (Tf2N) anion. These liquids exhibited thermochromism based on the monomer–dimer equilibrium of the cation.

A Series of [Fe-II(L)(2)](BF4)(2) compounds were structurally and physically characterized (L = 2,6-bis(2-methylthiazol-4-yl)pyridine). A crystal structure phase transformation from dihydtate compound 1 to anhydrous compound 3 through partially hydrated compounds 2 and 2' upon dehydration was found. Compounds 1 and 3 exhibited a gradual spin crossover (SCO) conversion, whereas compounds 2 and 2' demonstrated two-step and one-step abrupt SCO transitions, respectively. An X-ray single-crystal structural analysis revealed that one-dimensional and two-dimensional Fe cation networks linked by π stacking and sulfur-sulfur interactions. Were formed in 1 and 3, respectively. A thermodynamic analysis of the magnetic susceptibility for 1, 2', and 3 suggests that the enthalpy differences may govern SCO transition behaviors in the polymorphic compounds 2' and 3. A structural comparison between 1 and 3 indicates that the SCO behavior variations and crystal structure transformation in the present [Fe-II(L)(2)](BF4)(2) compounds can be interpreted by the relationship between the lattice enthalpies mainly arising froth Coulomb interactions between the Fe cations and BF4 anions as in typical ionic crystals.

Novel pseudopolymorphic Hdabco compounds with an Fe(III) complex anion, (Hdabco)[Fe(aznp)2]·CH2Cl2 1 and (Hdabco)[Fe(aznp)2]·0.5H2O 2 [dabco = 1,4-diazabicyclo[2.2.2]octane, H2aznp = (2′-hydroxyphenylazo)-2-hydroxynaphthalene], were prepared and characterized. The magnetic susceptibility for 1 and 2 revealed that both complexes were in a high-spin (HS) state in the whole temperature range and exhibited weak ferromagnetic interactions below 40 K. The crystal structural analyses suggested that strong N–H⋯O hydrogen bonding interactions between the Hdabco cation and [Fe(aznp)2] anion may induce the distortion of a coordination structure resulting in the HS complexes, whereas π-stacking interactions between the π-ligands in the [Fe(aznp)2] anion and additional C–H⋯N hydrogen bonding interactions between the Hdabco cation and [Fe(aznp)2] anion constructed a intermolecular interaction framework structure with one-dimensional channels. The thermogravimetry analysis for compound 1 indicated the adsorption of a water molecule took place after the desorption of a dichloromethane molecule. This transformation of 1 into 2 proved to proceed in a single-crystal-to-single-crystal way by powder X-ray diffractions and single crystal X-ray structural analysis.

A novel neutral heteroleptic FeIII complex from two kinds of π-extended tridentate ligands was designed and prepared. The π-ligands formed a three-dimensional purely pi-stacking interaction network. The present complex proved to be the first neutral spin-crossover (SCO) FeIII complex with a N3O3 coordination sphere exhibiting an abrupt SCO transition with a thermal hysteresis of 10 K and the light-induced excited spin-state trapping effect.

There are various thermochromic materials, though liquid thermochromic materials are less common. To produce functional thermochromic liquids, we have designed ionic liquids based on cationic nickel complexes with ether side chains, [Ni(acac)(Me2NC2H4NR1R2)]Tf2N ([1]Tf2N: R1 = C3H6OEt, R2 = Me, [2]Tf2N: R1 = C3H6OMe, R2 = Me, [3]Tf2N: R1 = R2 = C3H6OMe), where acac = acetylacetonate and Tf2N = (F3CSO2)2N−. The side chains (R1, R2) can moderately coordinate to the metal center, enabling temperature-dependent coordination equilibrium in the liquid state. [1]Tf2N is a liquid at room temperature. [2]Tf2N is obtained as a solid (Tm = 352.7 K) but remains liquid at room temperature after melting. [3]Tf2N is a solid with a high melting point (Tm = 422.3 K). These salts display thermochromism in the liquid state, colored red at high temperatures and orange, light blue, or bluish green at lower temperatures, exhibiting concomitant changes in the magnetic properties. This phenomenon is based on temperature-dependent equilibrium between a square-planar diamagnetic species and a paramagnetic species with intramolecular ether coordination.

To develop a new spin-crossover functional material, a magnetic hybrid compound [Fe(qsal)(2)][Ni(mnt)(2)] was designed and synthesized (Hqsal = N-(8-quinolyl)salicylaldimine, mnt = maleonitriledithiolate). The temperature dependence of magnetic susceptibility suggested the coexistence of the high-spin (HS) Fe(III) cation and pi-radical anion at room temperature and a magnetic transition below 100 K. The thermal variation of crystal structures revealed that strong pi-stacking interaction between the pi-ligand in the [Fe(qsal)(2)] cation and [Ni(mnt)(2)] anion induced the distortion of an Fe(III) coordination structure and the suppression of a dimerization of the [Ni(mnt)(2)] anion. Transfer integral calculations indicated that the magnetic transition below 100 K originated from a spin-singlet formation transformation in the [Ni(mnt)(2)] dimer. The magnetic relaxation of Mossbauer spectra and large thermal variation of a g-value in electron paramagnetic resonance spectra below the magnetic transition temperature implied the existence of a magnetic correlation between d-spin and pi-spin.

We explore the electrical and magnetic properties of a fractal assembly of Josephson junctions with transparent interfaces. For this purpose, we employ an $\mathrm{Mg}/\mathrm{MgO}/\mathrm{Mg}{\mathrm{B}}_{2}$ nanocomposite with \ensuremath{\sim}16 vol. % of $\mathrm{Mg}{\mathrm{B}}_{2}$ nanograins, which are distributed in a fractal manner in the normal matrix. Irrespective of the low volume fraction of $\mathrm{Mg}{\mathrm{B}}_{2}$ nanograins, the nanocomposite behaves as a bulk-like superconductor, i.e., zero resistivity, perfect diamagnetism, and strong vortex pinning. Thus, a global Josephson phase coherence is achieved in the nanocomposite. The lower (${H}_{\mathrm{c}1\mathrm{J}}$) and higher (${H}_{\mathrm{c}2\mathrm{J}}$) critical fields of the Josephson network are exceptionally high (${H}_{\mathrm{c}1\mathrm{J}}=96\phantom{\rule{0.16em}{0ex}}\mathrm{Oe}$ and ${H}_{\mathrm{c}2\mathrm{J}}=83.5\phantom{\rule{0.16em}{0ex}}\mathrm{kOe}$) as compared to those reported previously for granular superconductors. This will give an example of robust macroscopic superconducting coherence derived from long-range proximity coupling among fractally distributed superconducting nanograins through quantum interference of Andreev quasiparticles. Transverse-field muon spin rotation measurements reveal that the mean internal field in the superconducting mixed state increases with decreasing temperature below which the Josephson phase coherence sets in, opposite to the diamagnetic response observed in magnetization measurements. This unusual behavior implies a highly disordered and fluctuating nature of the Josephson vortices in the present superconducting nanocomposite.

Decamethyl- and octamethyl-ferrocenium salts of FnTCNQ (n = 1, 2) were prepared and their crystal structures characterized. The 2,5-F2TCNQ salts [Fe(C5Me5)2](2,5-F2TCNQ) (1) and [Fe(C5Me4H)2](2,5-F2TCNQ) (2) exhibit one-dimensional …[D]+[A]−[D]+[A]−… mixed-stack structures, while the salts with polar acceptors [Fe(C5Me5)2][A] (A = F1TCNQ (3), 2,3-F2TCNQ (4), 2,6-F2TCNQ (5)) and [Fe(C5Me4H)2][A] (A = 2,3-F2TCNQ (6), 2,6-F2TCNQ (7)) consist of [D]+[A2]2−[D]+ units involving a diamagnetic dimer of the acceptors. These salts are isomorphous to the corresponding TCNQ salts. 1 and 2 exhibit small ferromagnetic interactions at low temperatures. 1 undergoes an antiferromagnetic phase transition at TN = 3.9 K, which is higher than TN = 2.1 K of the metamagnetic polymorph of [Fe(C5Me5)2](TCNQ).

Alkali metal salts of 7,7′,8,8′-tetracyanoquinodimethane (TCNQ) reversibly absorb iodine forming the ternary salts M(TCNQ)I (M = Li, Na, K) and M2(TCNQ)3I2 (M = Rb). The ternary salts are also obtained by solid-state reactions of TCNQ with alkali iodides. These salts are paramagnetic and have high electrical conductivities, ∼10−1 S cm−1, for compacted pellets, whereas the alkali metal salts of TCNQ are diamagnetic insulators. The ternary salts further absorb iodine to give over-doped salts M(TCNQ)In (n ≈ 6, M = Na, K), which gradually release iodine to give M(TCNQ)I. In contrast, the solid-state reaction of F4TCNQ and sodium iodide produces Na(F4TCNQ), which does not exhibit iodine absorption.

The single crystal of RuAs obtained by Bi-flux method shows obvious successive metal-insulator transitions at T_MI1~255 K and T_MI2~195$ K. The X-ray diffraction measurement reveals a formation of superlattice of 3x3x3 of the original unit cell below T_MI2, accompanied by a change of the crystal system from the orthorhombic structure to the monoclinic one. Simple dimerization of the Ru ions is nor seen in the ground state. The multiple As sites observed in nuclear quadrupole resonance (NQR) spectrum also demonstrate the formation of the superlattice in the ground state, which is clarified to be nonmagnetic. The divergence in 1/T_1 at T_MI1 shows that a symmetry lowering by the metal-insulator transition is accompanied by strong critical fluctuations of some degrees of freedom. Using the structural parameters in the insulating state, the first principle calculation reproduces successfully the reasonable size of nuclear quadrupole frequencies for the multiple As sites, ensuring the high validity of the structural parameters. The calculation also gives a remarkable suppression in the density of states (DOS) near the Fermi level, although the gap opening is insufficient. A coupled modulation of the calculated Ru d electron numbers and the crystal structure proposes a formation of charge density wave (CDW) in RuAs. Some lacking factors remain, but it shows that a lifting of degeneracy protected by the non-symmorphic symmetry through the superlattice formation is a key ingredient for the metal-insulator transition in RuAs., Comment: 10 pages, 10 figures

We have made a survey of ceramics for the inner parts of the transmission-type pressure cell to achieve the high pressure and the high transmission in THz range. By using the optimal combination of ZrO$_{2}$-based ceramic and Al$_{2}$O$_{3}$ ceramic, we have succeeded in obtaining the pressure up to 1.5 GPa and the frequency region up to 700 GHz simultaneously. We show the high-pressure ESR results of Shastry-Sutherland compound SrCu$_{2}$(BO$_{3}$)$_{2}$ as an application. We observed the direct ESR transition modes between the singlet ground state and the triplet excited states up to the pressure of 1.51 GPa successfully, and obtained the precise pressure dependence of the gap energy. The gap energy is directly proved to be suppressed by the pressure. Moreover, we found that the system approaches the quantum critical point with pressure by comparing the obtained data with the theory. This result also shows the usefulness of high-pressure ESR measurement in THz region to study quantum spin systems.

High field ESR studies of spin gap systems F 2 PNNNO and KCuCl 3 have been performed. The broadening of the linewidth in F 2 PNNNO is observed near the start of the 1/2 plateau but not near the entrance of the field induced order at 9 T. The possible origin is discussed. The reduction of the spin gap by pressure in KCuCl 3 is observed directly by high field ESR under pressure. The result is discussed in connection with the theory by Matsumoto et al.

Magnetization, specific heat, and electrical resistivity measurements have been performed on polycrystalline samples of a new cubic compound, Ce6Pd13Zn4. This compound exhibits metallic behavior and is classified as a Kondo-lattice system. The trivalent Ce ions are responsible for the antiferromagnetic transition at TN = 3.3 K and the phase transition at \(T'_{\text{N}} = 1.3\) K with the formation of superzone gaps. The increase in magnetic susceptibilities below TN and the considerably large value of the specific heat divided by temperature (1.25 J·Ce-mol−1·K−2) imply the existence of non-ordered Ce magnetic moments due to the geometrical frustration on the octahedral Ce sublattice.

The microscopic magnetic properties of high-quality GdN thin films have been investigated by electron spin resonance (ESR) and ferromagnetic resonance (FMR) measurements. Detailed temperature dependence ESR measurements have shown the existence of two ferromagnetic components at lower temperatures, which was not clear from the previous magnetization measurements. The temperature, where the resonance shift occurs for the major ferromagnetic component, seems to be consistent with the Curie temperature obtained from the previous magnetization measurement. On the other hand, the divergence of line width is observed around 57 K for the minor ferromagnetic component. The magnetic anisotropies of GdN thin films have been obtained by the analysis of FMR angular dependence observed at 4.2 K. Combining the X-ray diffraction results, the correlation between the magnetic anisotropies and the lattice constants is discussed.

A paramagnetic ferrocenium-based ionic liquid that exhibits a magnetic memory effect coupled with a liquid–solid phase transformation has been developed. Based on field alignment of the magnetically anisotropic ferrocenium cation, the magnetic susceptibility in the solid state can be tuned by the weak magnetic fields (

In a frustrated J_1-J_2 chain with the nearest-neighbor ferromagnetic interaction J_1 and the next-nearest-neighbor antiferromagnetic interaction J_2, novel magnetic states such as a spin-nematic state are theoretically expected. However, they have been rarely examined in experiments because of the difficulty in obtaining suitable model compounds. We show here that the quasi-one-dimensional antiferromagnet NaCuMoO_4(OH), which comprises edge-sharing CuO_2 chains, is a good candidate J_1-J_2 chain antiferromagnet. The exchange interactions are estimated as J_1 = - 51 K and J_2 = 36 K by comparing the magnetic susceptibility, heat capacity, and magnetization data with the data obtained using calculations by the exact diagonalization method. High-field magnetization measurements at 1.3 K show a saturation above 26 T with little evidence of a spin nematic state expected just below the saturation field, which is probably due to smearing effects caused by thermal fluctuations and the polycrystalline nature of the sample., 6 pages, 4 figures

Chloroplasts originated from cyanobacteria through endosymbiosis. The original cyanobacterial endosymbiont evolved to adapt to the biochemically rich intracellular environment of the host cell while maintaining its photosynthetic function; however, no such process has been experimentally demonstrated. Here, we show the adaptation of a model cyanobacterium, Synechocystis sp. PCC 6803, to a biochemically rich environment by experimental evolution. Synechocystis sp. PCC 6803 does not grow in a biochemically rich, chemically defined medium because several amino acids are toxic to the cells at approximately 1 mM. We cultured the cyanobacteria in media with the toxic amino acids at 0.1 mM, then serially transferred the culture, gradually increasing the concentration of the toxic amino acids. The cells evolved to show approximately the same specific growth rate in media with 0 and 1 mM of the toxic amino acid in approximately 84 generations and evolved to grow faster in the media with 1 mM than in the media with 0 mM in approximately 181 generations. We did not detect a statistically significant decrease in the autotrophic growth of the evolved strain in an inorganic medium, indicating the maintenance of the photosynthetic function. Whole-genome resequencing revealed changes in the genes related to the cell membrane and the carboxysome. Moreover, we quantitatively analyzed the evolutionary changes by using simple mathematical models, which evaluated the evolution as an increase in the half-maximal inhibitory concentration (IC50) and estimated quantitative characteristics of the evolutionary process. Our results clearly demonstrate not only the potential of a model cyanobacterium to adapt to a biochemically rich environment without a significant decrease in photosynthetic function but also the properties of its evolutionary process, which sheds light of the evolution of chloroplasts at the initial stage.

Recent development of the high-field facility in Kobe University is presented. We installed a 3 kV, 100 kJ capacitor bank, this is four times larger in energy than the previous one, and we achieved 42 T recently using a Cu–Ag pulsed magnet. Recent high-field ESR studies of quantum spin systems such as high pressure phase (VO)2P2O7 will be presented. The high-pressure phase of (VO)2P2O7 is the S= 1 2 bond alternating antiferromagnet; we found an anomaly in the ESR mode of the high-pressure phase (VO)2P2O7 single crystal at 20 T by observing the frequency dependence at 4.2 K. Finally, we refer to our new development of the high-field ESR system under high pressure. We developed a compact pressure cell with sapphire window which fits into our pulsed magnet. The ESR result using this pressure cell will be presented.

Many efforts are under way to control the structure of heterointerfaces in nanostructured composite materials for designing functionality and engineering application. However, the fabrication of high-quality heterointerfaces is challenging because the crystal/crystal interface is usually the most defective part of the nanocomposite materials. In this work, we show that fully dense insulator (MgO)/semiconductor(Mg2Si)/superconductor(MgB2) nanocomposites with atomically smooth and continuous interfaces, including epitaxial-like MgO/Mg2Si interfaces, are obtained by solid phase reaction between metallic magnesium and a borosilicate glass. The resulting nanocomposites exhibit a semiconductor-superconducting transition at 36 K owing to the MgB2 nanograins surrounded by the MgO/Mg2Si matrix. This transition is followed by the intergrain phase-lock transition at ∼24 K due to the construction of Josephson-coupled network, eventually leading to a near-zero resistance state at 17 K. The method not only provides a s...

To investigate the π-extension effect on an unusual negative-charged spin crossover (SCO) FeIII complex with a weak N2O4 first coordination sphere, we designed and synthesized a series of anionic FeIII complexes from a π-extended naphthalene derivative ligand. Acetonitrile-solvate tetramethylammonium (TMA) salt 1 exhibited an SCO conversion, while acetone-solvate TMA salt 2 was in a high-spin state. The crystal structural analysis for 2 revealed that two-leg ladder-like cation-anion arrays derived from π-stacking interactions between π-ligands of the FeIII complex anion and Coulomb interactions were found and the solvated acetone molecules were in one-dimensional channels between the cation-anion arrays. A desolvation-induced single-crystal-to-single-crystal transformation to desolvate compound 2’ may be driven by Coulomb energy gain. Furthermore, the structural comparison between quasi-polymorphic compounds 1 and 2 revealed that the synergy between Coulomb and π-stacking interactions induces a significant distortion of coordination structure of 2.

We investigate the interaction between superconductivity and defect-induced d0 ferromagnetism using a composite consisting of MgB2 and MgO nanocrystals. The composite exhibits a ferromagnetic hysteresis behavior in the temperature region from 40 to 300 K. Defective MgO nanocrystals (∼20 nm) embedded in the composite are considered to be responsible for the observed ferromagnetism. The zero field cool and field cool magnetization curves show that the superconducting transition occurs at Tc = 38.6 K, in agreement with Tc of pure MgB2. In the temperature region from Tc to 0.9Tc (∼35 K), the magnetization hysteresis curves show a superposition of ferromagnetic (F) and superconducting (S) signals. When the temperature of the system is decreased below 0.65Tc (∼25 K), the S signals dominate over the F signals. The resulting magnetic hysteresis loops are highly asymmetric and the descending filed branch is nearly flat, as predicted in the case of surface pinning. At temperatures below 0.5Tc (∼20 K), a sharp peak ...

The electron spin resonance (ESR) system which covers the magnetic field region up to 16 T, the quasicontinuous frequency region from 60 to 700 GHz, the temperature region from 1.8 to 4.2 K, and the hydrostatic pressure region up to 1.1 GPa has been developed. This is the first pulsed high-field and multifrequency ESR system with the pressure region over 1 GPa as far as we know. Transmission ESR spectra under hydrostatic pressure can be obtained by combining a piston-cylinder-type pressure cell and the pulsed magnetic field ESR apparatus. The pressure cell consists of a NiCrAl cylinder and sapphire or zirconia inner parts. The use of sapphire or zirconia as inner parts enables us to observe ESR under pressure because these inner parts have high transmittance for the electromagnetic wave with millimeter and submillimeter wavelengths. We have successfully applied this system for the pressure dependence measurements of an isolated spin system NiSnCl(6)6H(2)O up to 1.1 GPa. It was found that the single ion anisotropy parameter D of this compound strongly depends on pressure. The parameter D is approximately proportional to the pressure up to 0.75 GPa, and the relation between D and the pressure can be used for the pressure calibration of this high-field and high-pressure ESR system.