Magnetic Measurements Research Articles

Single-molecule Magnets (SMM) spin channels connecting FeMn antiferromagnet and NiFe ferromagnetic electrodes of a tunnel junction

The integration of single-molecule magnets (SMMs) into magnetic tunnel junctions (MTJs) offers significant potential for advancing molecular spintronics, particularly for next-generation memory devices, quantum computing, and energy storage technologies such as solar cells. In this study, we present the first demonstration of SMM-induced spin-dependent properties in an antiferromagnet-based MTJ molecular spintronic device (MTJMSD). We engineered cross-junction-shaped devices comprising FeMn/AlOx/NiFe MTJs. The AlOx barrier thickness where the exposed junction edges meet was comparable to the SMM length, facilitating the incorporation of SMM molecules as spin channels for spin-dependent transport. The SMM channels enabled long-range magnetic moment ordering around molecular junctions, which were precisely engineered via fabrication processes. The SMM, composed of a [Mn6(μ3-O)2(H2N-sao)6(6-atha)2(EtOH)6] (H2N-saoH = salicylamidoxime, 6-atha = 6-acetylthiohexanoate) complex, featured thioester groups at the ends that upon hydrolysis they form bonds with the magnetic electrodes. SMM-treated junctions demonstrated a significant current enhancement, reaching up to 7 μA at an input voltage of 60 mV. Furthermore, SMM-doped junctions exhibited current stabilization in the μA range at lower temperatures, whereas the bare electrodes showed current suppression to the picoampere range. Magnetization measurements conducted at 55 K and 300 K on pillar-shaped devices revealed a reduction in magnetic moment at low temperatures. Additionally, Kelvin probe atomic force microscopy (KPAFM) measurements confirmed that SMM integration transformed the electronic properties over long ranges.These findings are attributed to the spin channels formed between magnetic metal electrodes, which enhance spin polarization at each magnetic electrode. Our research highlights the potential of using antiferromagnetic materials, characterized by minimal stray fields and zero net magnetization, to transform MTJMSD devices.

Influence of Mo dopants on the vibrational, emission, dielectric, electrical, and magnetic properties of combustion synthesized ZnFe2O4 nanostructures for optoelectronic and spintronic applications

This report investigates the dielectric and magnetic behavior of Molybdenum (Mo)-incorporated ZnFe2O4 prepared via combustion route with different dopant concentrations (0.0, 0.1, 0.25, 0.5, 0.75, and 1.0 wt.%). XRD patterns reveal the cubic spinel structures with a slight increase in lattice constant while replacing Mo at Fe sites. Mo doped induced lattice constant increase from 8.444 to 8.469 Å coupled with a significant increase in density. Raman spectroscopy reveals a decrement in the peak broadening of the A1g mode at higher Mo concentrations, indicating longer phonon lifetimes. Scanning electron microscopy (SEM) and EDX analysis confirm the agglomerated pseudo-spherical structures with uniform elemental distribution over the surface. Further, the dielectric constant values exhibit a slightly decreasing trend with increasing frequency, and the mechanisms were discussed based on the intrinsic polarization due to the charge imbalance between Fe3+ and Fe2+ states. Further, the magnetic measurements confirm the soft magnetic behavior with saturation magnetization ranging from 13.72 to 14.61 emu/g and coercivity between 07 (Oe) to 44 (Oe). The overall findings demonstrate that Mo doping in ZnFe₂O₄ significantly modifies the dielectric and magnetic properties, making it a promising material for various technological applications.

Synthesis, Characterization and In-vitro Antibacterial Activity Studies of Oxovanadium (IV) Complexes of α-Amino Acid Schiff Bases and 1,10-Phenanthroline Ligands

Oxovanadium(IV) complexes of the type [VO(L)(phen)] (VO-1 to VO-5) have been synthesized and characterized by FTIR and UV-Vis spectra, molar conductance, melting points, and magnetic susceptibilities measurements, where L= N-salicylidene-β-alanine (sal-ala), N-salicylidene-glycine (sal-gly), N-salicylidene-DL-β-phenylalanine (sal-pheala), N-salicylidene-leucine (sal-leu), and N-salicylidene-DL-methionine (sal-met), and phen is 1,10-phenanthtroline. The infrared spectral data reveals that the tridentate nature of the amino acid-based Schiff base ligand and the coordination of the ligand through azomethine nitrogen, phenolic oxygen and carboxylate oxygen with vanadyl (VO2+) ion. All of these complexes were determined to be non-electrolyte in nature, according to conductivity measurements. The magnetic moment measurements have been attributed that these complexes are paramagnetic and have d1 configuration of vanadium (IV) ion. The antimicrobial activity of the synthesized complexes was evaluated against four pathogenic bacteria viz. Escherichia coli, Proteus vulgaris, Bacillus subtilis and Staphylococcus aureus.

Structure and Magnetic Properties of Fe<sub>3</sub>O<sub>4</sub>/C Composites Synthesized from Wheat Straw

The porous structure and magnetic properties of nanostructured Fe3O4/C composites based on wheat straw were investigated in this work. The synthesis was carried out by a one- and two-step method using FeCl3 and ZnCl2 as activating agents. X-ray diffraction methods have shown the presence of an additional phase of magnetite Fe3O4 in both synthesized composites, along with the amorphous carbon phase. Magnetic measurements have shown that the composite synthesized in one step has better magnetic properties, in particular, a higher specific saturation magnetisation. However, the samples of the composite synthesized in two steps are characterised by a higher content of micropores and mesopores, which causes an increase in the specific surface area to 884 m2/g compared to 405 m2/g for the samples synthesized in one step. Based on the dependence of the coercive force on the particle diameter in Fe3O4 dispersions, it was found that the average size of the magnetite particles is ~25 nm for both synthesized magnetoresponsive composites.

The Arpu Kuilpu meteorite: In‐depth characterization of an H5 chondrite delivered from a Jupiter Family Comet orbit

AbstractOver the Nullarbor Plain in South Australia, the Desert Fireball Network detected a fireball on the night of June 1, 2019 (7:30 pm local time), and 6 weeks later recovered a single meteorite (42 g) named Arpu Kuilpu. This meteorite was then distributed to a consortium of collaborating institutions to be measured and analyzed by a number of methodologies including SEM‐EDS, EPMA, ICP‐MS, gamma‐ray spectrometry, ideal gas pycnometry, magnetic susceptibility measurement, μCT, optical microscopy, and accelerator and noble gas mass spectrometry techniques. These analyses revealed that Arpu Kuilpu is an unbrecciated H5 ordinary chondrite, with minimal weathering (W0‐1) and minimal shock (S2). The olivine and pyroxene mineral compositions (in mole%) are Fa: 19.2 ± 0.2 and Fs: 16.8 ± 0.2, further supporting the H5 type and class. The measured oxygen isotopes are also consistent with an H chondrite (δ17O‰ = 2.904 ± 0.177; δ18O‰ = 4.163 ± 0.336; Δ17O‰ = 0.740 ± 0.002). Ideal gas pycnometry measured bulk and grain densities of 3.66 ± 0.02 and 3.77 ± 0.02 g cm−3, respectively, yielding a porosity of 3.0% ± 0.7. The magnetic susceptibility of this meteorite is log χ = 5.16 ± 0.08. The most recent impact‐related heating event experienced by Arpu Kuilpu was measured by 40Ar/39Ar chronology to be 4467 ± 16 Ma, while the cosmic ray exposure age is estimated to be between 6 and 8 Ma. The noble gas isotopes, radionuclides, and fireball observations all indicate that Arpu Kuilpu's meteoroid was quite small (maximum radius of 10 cm, though more likely between 1 and 5 cm). Although this meteorite is a rather ordinary ordinary chondrite, its prior orbit resembled that of a Jupiter Family Comet (JFC) further lending support to the assertion that many cm‐ to m‐sized objects on JFC orbits are asteroidal rather than cometary in origin.

Influence of gadolinium doping on structural, optical, and magnetic properties of CuS nanostructures

To examine the effect of rare earth ions on CuS nanostructures, a series of Gadolinium-doped copper sulphide (Cu1-xGdxS) nanostructures were synthesized through the hydrothermal method. These nanostructures were prepared at x = 0, 1, 3, 5, and 7 at. % concentrations. The prepared samples’ structural, optical, and magnetic characteristics were investigated. Powder X-ray diffraction and Raman analysis were performed to examine the structural analysis of the samples and confirm the existence of a covellite phase hexagonal structure. XPS analysis was conducted to study the valence states. Observations of the surface morphology study from FESEM reveal the formation of flower-shaped structures resembling nanospheres, while at lower magnification nanoflakes were observed. Optical reflectance spectra were recorded using UV–Vis spectroscopy, which showed the increase in bandgap as the concentration of Gd rises. The fluorescence spectrophotometer was utilized for the analysis of room-temperature photoluminescence. The prepared samples showed significant emission peaks at 435 nm. Fluorescence lifetime studies were carried out to confirm the fluorescence decay of CuS nanostructures doped with Gd. Magnetic measurements revealed that prepared samples exhibit an unexpected superparamagnetic nature at room temperature.

Synthesis and Characterization of New Copper(II) Coordination Compounds with Methylammonium Cations

We synthesized four new copper(II) complexes with acetato and chlorido ligands and methylammonium (MA), dimethylammonium (DMA), and tetramethylammonium (TMA) counterions: (MA)4[Cu2Ac4Cl2]Cl2·2H2O (1), (DMA)2[Cu2Ac4Cl2] (2), (DMA)4[Cu2Ac4Cl2]Cl2·2H2O (3), and (TMA)5[Cu2Ac4Cl]Cl4·4H2O (4). All compounds were characterized by single-crystal X-ray diffraction, magnetic measurements, FTIR spectroscopy, and thermogravimetric analysis. Complexes 1, 2, and 3 consist of a dinuclear coordination anion [Cu2(Ac)4Cl2]2− with bridging acetato ligands arranged in a paddle-wheel conformation and square-pyramidal coordination around Cu(II) atoms, while the coordination anion in compound 4 is a polymeric chain, parallel to the c axis, with Cu2(Ac)4 units connected through bridging chlorido ligands. Magnetic measurements carried out between 2 K and 300 K indicate strong antiferromagnetic interactions between Cu(II) ions. The effective magnetic moments range from 1.94 μB to 2.21 μB, exceeding the spin-only value for Cu(II) ions (μeff=1.73 μB) and suggesting significant orbital contributions to the magnetic moment. Thermogravimetric analysis of all complexes showed a multistep decomposition behavior yielding elemental copper as the final product.

Thermal expansion, quasi-metamagnetism and spin-reorientation in Fe7Se8 substituted with chromium

The properties of the selenide compound Fe7Se8 with a layered crystal structure of the NiAs type are strongly influenced by substitutions and the distribution of vacancies. The Cr-substituted compound Fe6.5Cr0.5Se8 was obtained in single-crystalline form and studied by x-ray diffraction, energy-dispersive x-ray spectroscopy, thermal expansion and magnetization measurements. It was observed that the partial replacement of iron with chromium led to a twofold decrease in spontaneous volume magnetostriction due to changes in competing magnetoelastic contributions to thermal expansion along and perpendicular to the c axis of the crystal. The replacement of iron with chromium slightly decreases the Néel temperature (from 440 to 435 K) and significantly enhances the critical temperature of spin reorientation transition Tsr (from 115 to 160 K), apparently due to a change in the crystal electric field. Below 160 K, the Fe6.5Cr0.5Se crystal is found to exhibit metamagnetic-like behavior of the magnetization when the magnetic field is applied along the c axis. A jump-like change of the magnetization at a critical field up to ∼10 kOe is attributed to the presence of pinning centers of domain walls presumably due the ordering of chromium atoms substituting iron in cationic layers.

White Matter Magnetic Resonance Diffusion Measures in Multiple Sclerosis with Overactive Bladder.

Lower urinary tract (LUT) symptoms are reported in more than 80% of patients with multiple sclerosis (MS), most commonly an overactive bladder (OAB). The relationship between brain white matter (WM) changes in MS and OAB symptoms is poorly understood. We aim to evaluate (i) microstructural WM differences across MS patients (pwMS) with OAB symptoms, patients without LUT symptoms, and healthy subjects using diffusion tensor imaging (DTI), and (ii) associations between clinical OAB symptom scores and DTI indices. Twenty-nine female pwMS [mean age (SD) 43.3 years (9.4)], including seventeen with OAB [mean age (SD) 46.1 years (8.6)] and nine without LUT symptoms [mean age (SD) 37.5 years (8.9)], and fourteen healthy controls (HCs) [mean age (SD) 48.5 years (20)] were scanned in a 3T MRI with a DTI protocol. Additionally, clinical scans were performed for WM lesion segmentation. Group differences in fractional anisotropy (FA) were evaluated using tract-based spatial statistics. The Urinary Symptom Profile questionnaire assessed OAB severity. A statistically significant reduction in FA (p = 0.004) was identified in microstructural WM in pwMS, compared with HCs. An inverse correlation was found between FA in frontal and parietal WM lobes and OAB scores (p = 0.021) in pwMS. Areas of lower FA, although this did not reach statistical significance, were found in both frontal lobes and the rest of the non-dominant hemisphere in pwMS with OAB compared with pwMS without LUT symptoms (p = 0.072). This study identified that lesions affecting different WM tracts in MS can result in OAB symptoms and demonstrated the role of the WM in the neural control of LUT functions. By using DTI, the association between OAB symptom severity and WM changes were identified, adding knowledge to the current LUT working model. As MS is predominantly a WM disease, these findings suggest that regional WM involvement, including of the anterior corona radiata, anterior thalamic radiation, superior longitudinal fasciculus, and superior frontal-occipital fasciculus and a non-dominant prevalence in WM, can result in OAB symptoms. OAB symptoms in MS correlate with anisotropy changes in different white matter tracts as demonstrated by DTI. Structural impairment in WM tracts plays an important role in LUT symptoms in MS.

Design, synthesis, characterization, theoretical calculations, molecular docking studies, and biological evaluation of new Fe(II) and Cu(II) complexes of 2-acetylpyridine derivative sulfonyl hydrazone Schiff base

Sulfonylhydrazones and their metal complexes are known to have potential biological activity. In this study, new Fe(II) (1) and Cu(II) (2) complexes of the 2-acetylpyridine derivative sulfonyl hydrazone (LH) were prepared. The new metal complexes were characterized by elemental analysis, IR spectroscopy, UV spectroscopy, and magnetic moment measurements. The molecular structure of (2) was elucidated by X-ray diffraction analysis, and the crystal package was obtained in three-dimensional space. To support the intermolecular interactions obtained from the X-ray diffraction results, Hirshfeld surface analysis and two-dimensional fingerprint maps of (2) were generated. The optimized molecular structures, total energies, molecular orbital energy values, molecular electrostatic potential maps, percentage distributions of the atomic orbitals to the molecular orbital energy levels, and global reactivity parameters of LH, 1, and 2 are obtained by using DFT/B3LYP/6–311G(d, p) for LH and DFT/B3LYP/LanL2DZ for 1 and 2 is 1:2. Elemental analysis showed that the stoichiometric metal/ligand ratio for 1 and 2. All data indicate that the ligand coordinates with the metal atoms via pyridine imine /nitrogens and sulfonyl oxygen. The well-diffusion approach was also used to test the antibacterial properties of the ligand and complexes against harmful microbes. The compounds were tested for DNA cleavage using agarose gel electrophoresis. Complex 1 was found to be effective on the plasmid DNA of pBR322. Finally, molecular docking studies of LH, 1, and 2 with A-DNA (PDB ID:3V9D), and B-DNA (PDB ID:1BNA) were presented to compare the experimental and theoretical results.

A low-cost electronic and optical system for magnetic hyperthermia experimental studies

Magnetic hyperthermia is an alternative to treatments such as chemotherapy and radiotherapy that employs the heat generated by magnetic nanoparticles under the influence of a magnetic field to kill cancer cells while ideally causing no harm to healthy tissues. A low-cost magnetic hyperthermia investigation platform with commercially available and easy-to-assemble parts was presented to provide and expand research in this area for a larger scientific community. The magnetic hyperthermia measurement system consists of three main parts: a designed thermally insulated sample holder, a commercial 88 kHz magnetic induction heater, and a custom-built fiber optic based refractometer as temperature sensor. The system was tested with commercial EFH-1 magnetic fluids. Time dependent temperature changes were measured for applied magnetic fields of 3.5 kA/m, 4.8 kA/m, and 6.0 kA/m. The corresponding specific loss power values were calculated as 0.28 W/g, 0.51 W/g, and 0.79 W/g, respectively. Intrinsic loss power of commercial ferrofluid was determined as 0.25 ± 0.01 nHm2/kg, found to be comparable to the results of specialized commercial magnetic hyperthermia systems. The results show that the system can easily be used for hyperthermia demonstrations for educational purposes as well as in convenient scientific research with proper calibration.

Single crystal growth and magnetic properties in triangular chain compound Ni2SiO4

Sub-centimeter-scale Ni2SiO4 single crystals were grown by a flux method with K2MoO4 as the flux. The obtained crystals exhibit high quality and were characterized using X-ray diffraction, chemical analysis, and magnetic properties, including high magnetic field (H) magnetization (M) measurements. The results of magnetic susceptibility and specific heat of a single crystal reveal significant magnetic anisotropy and antiferromagnetic ordering below TN = 30 K. High-field magnetization up to 43 T of polycrystalline shows six magnetic phase transitions at H1 = 14 T, H2 = 18.4 T, H3 = 23 T, H4 = 29 T, H5 = 32.5 T, and H6 = 37 T, forming a complex magnetic phase diagram with seven phases. Notably, the M exhibits a linear relationship with H during phases V (H4 < H < H5) and VII (H > H6), showing intercepts at 0 and half of magnetization saturation respectively, implying the presence of a spin flop transition and a 1/2 magnetization plateau. These novel phenomena in such a triangular chain system highlight complex physical nature, making Ni2SiO4 a promising candidate for studying intricate magnetic interactions.

Elucidating correlation-driven insulating state in an effective spin—½ antiferromagnet NdVO4

TheJeff= ½ state: a result of interplay of strong electronic correlations (U) with spin-orbit coupling (SOC) and crystal field splitting, offers a platform in the research of quantum materials. In this context, 4frare-earth based materials offer a fertile playground. Here, strong experimental and theoretical evidences for aJeff= ½ state is established in a three-dimensional spin system NdVO4. Magnetic measurements show the signatures of a SOC drivenJeff= ½ state along with the presence of antiferromagnetic (AFM) interaction between Nd3+moments, whereas, heat capacity reveals the presence of an AFM ordering around 0.8 K, within this state. An entropy of Rln2 (equivalent toJ= ½) is released around 4 K which implies the presence ofJeff= ½ state at low temperatures. Total energy calculations within the density functional theory (DFT) framework reflect the central role of SOC in driving the Nd3+ions to host such a state with AFM correlations between them, which is in agreement with experimental results. Further, DFT + SOC calculations with and without the inclusion ofU, points that electron-electron correlations give rise to the insulating state making NdVO4a potential candidate forU-driven correlated Mott insulator.

Eco-friendly synthesis of nano ferrites for effective dye degradation and enhanced antimicrobial protection

This study investigates the synthesis of cobalt and nickel ferrite NPs using Araucaria heterophylla resin as a bio- template and nitrate salts of cobalt, nickel, and iron as precursors.The resulting spinel systems exhibit efficient degradation of organic dyes, including methylene blue and rhodamine-B, and demonstrate excellent reusability. The NPs antibacterial efficacy against pathogenic bacteria, such as Staphylococcus aureus, Bacillus subtilis, Escherichia coli, and Salmonella paratyphi, was also evaluated. Comprehensive characterization of the nanomaterials was performed using FT-IR, XRD, SEM, TEM, EDX, and VSM techniques. Magnetic measurements revealed the ferromagnetic nature of cobalt ferrites and the superparamagnetic nature of nickel ferrites, with reduced saturation magnetization and coercivity compared to bulk materials due to the quantum size effect. The nano-formulated ferrites exhibited superior antibacterial activity, highlighting their potential for water treatment applications. This study underscores the importance of removing dye contaminants from wastewater before discharge into aquatic ecosystems.

Effect of Synthesis Conditions on the Composition, Local Structure and Electrochemical Behavior of (Cr,Fe,Mn,Co,Ni)3O4 Anode Material

AbstractDisordered high entropy spinels (HES) (Cr,Fe,Mn,Co,Ni)3O4 were obtained by solid‐state synthesis and co‐precipitation using various powder precursors. They were characterized by a complex of physico‐chemical methods and investigated as anode materials for lithium‐ion batteries (LIBs). According to XRD and TEM data, the materials are single‐phase. The structural characterization of the samples obtained at 773, 973, and 1273 K was determined using Raman and Mössbauer spectroscopy, and magnetic measurements. The degree of spinel inversion and lattice distortion (microstrains) decrease with increasing synthesis temperature, while the crystallite size increases. The insufficient nickel content in the samples ensures a more uniform distribution of iron cations in both sublattices, which leads to an increase in the lattice parameters and has a positive effect on the de‐/lithiation. Repeated ball‐milling of HES material, prepared by co‐precipitation, increases its specific capacity from 284 mAh g−1 to 492 mAh g−1 at a current density of 100 mA g−1 after 25 cycles. Besides, the smaller crystallite size reduces the volume changes in the materials during de‐/lithiation.

Freezing of short-range ordered antiferromagnetic clusters in the CrFeTi2O7system.

We report on the CrFeTi2O7(CFTO) system using a combination of x-ray diffraction, dc magnetization, ac susceptibility, specific heat and neutron diffraction measurements. CFTO is seen to crystallize in a monoclinic P21/a symmetry. It shows a glassy freezing at Tf ~ 22 K, characterized by the observation of bifurcation between ZFC and FC χ (T) curves, frequency dispersion across Tf in ac susceptibility, and follows Vogel-Fulcher and power law type critical dynamics, very slow relaxation of iso-thermal remanent magnetization with time and the absence of an anomaly in the temperature dependence of specific heat measurements. The microscopic neutron diffraction analysis of CFTO not only confirms the absence of long-range antiferromagnetic ordering but also exhibits diffuse scattering due to the presence of short-range ordered antiferromagnetically correlated spin clusters.&#xD.

Fiber optic magnetic field sensor based on a magnetic-fluid-induced phase-shift FLRD

A magnetic field sensing system based on a phase-shift fiber loop ring-down (FLRD) technique and multi-mode interferometer (MI) coated with magnetic fluid (MF) is proposed and demonstrated. The MI is constructed by splicing a segment of no-core fiber between two sections of single-mode fibers, which is then immersed in MF to serve as a sensing head with the advantages of simple fabrication and specific magnetic sensitivity. Due to the magnetic refractive index tunable properties of the MF, the magnetic-field-dependent loss will be introduced in the fiber loop by the sensing head. Such magnetic-induced loss would be accumulated during the round trip of the optical carrier and reflected on the phase information of the modulated signal. The phase-shift changes with the applied magnetic field strength, enabling magnetic field sensing through phase-shift measurements. The sensing system is experimentally demonstrated and a sensitivity of 0.704×10−3deg/Gs in the linear region is achieved. Moreover, the stability and repeatability of the system are verified, leading to a promising method for magnetic field measurements.

A Novel Banana-Shaped Mixed-Metal Co/Fe Polyoxometalate Cluster.

The synthesis and characterization of a Co/Fe mixed-metal banana-shaped polyoxometalate with the formula [(Co2.5Fe0.5(H2O)PW9O34)2(PW6O26)]16- (Co5Fe) is reported. This transition-metal-substituted polyoxometalate readily assembles from its components in a one-pot reaction and crystallizes in the monoclinic space group P21/c. The structure of Co5Fe can be considered a double sandwich composed by two B-α-{Co2.5Fe0.5PW9O40} Keggin units, in which one coordinatively saturated octahedral metal position is equally occupied by Co(II) and Fe(III) ions with a 50% of site occupancy. These Keggin units are linked via a hexalacunary Keggin unit {PW6O26}. Single crystal X-ray diffraction and magnetic measurements support the proposed atom arrangement within the crystal structure. Magnetic measurements of these double trimeric unit {Co2.5Fe0.5O13}2 show a combination of antiferromagnetic interaction, the presence of spin frustration, and the first-order spin-orbit coupling Co(II) ions. Electrocatalytic water oxidation measurements show that Co5Fe displays low stability in both homogeneous and heterogeneous conditions. This is evidenced by the constant increase on the catalytic currents over time together with the appearance of polyoxometalate-derived electrode-bound species that can be responsible for the observed catalytic activity.

Tuning structural modulation and magnetic properties in metal-organic coordination polymers [CH3NH3]CoxNi1-x(HCOO)3.

Three solid solutions of [CH3NH3]CoxNi1-x(HCOO)3, with x = 0.25 (1), x = 0.50 (2) and x = 0.75 (3), were synthesized and their nuclear structures and magnetic properties were characterized using single-crystal neutron diffraction and magnetization measurements. At room temperature, all three compounds crystallize in the Pnma orthorhombic space group, akin to the cobalt and nickel end series members. On cooling, each compound undergoes a distinct series of structural transitions to modulated structures. Compound 1 exhibits a phase transition to a modulated structure analogous to the pure Ni compound [Cañadillas-Delgado, L., Mazzuca, L., Fabelo, O., Rodríguez-Carvajal, J. & Petricek, V. (2020). Inorg. Chem. 59, 17896-17905], whereas compound 3 maintains the behaviour observed in the pure Co compound reported previously [Canadillas-Delgado, L., Mazzuca, L., Fabelo, O., Rodriguez-Velamazan, J. A. & Rodriguez-Carvajal, J. (2019). IUCrJ, 6, 105-115], although in both cases the temperatures at which the phase transitions occur differ slightly from the pure phases. Monochromatic neutron diffraction measurements showed that the structural evolution of 2 diverges from that of either parent compound, with competing hydrogen bond interactions that drive the modulation throughout the series, producing a unique sequence of phases. It involves two modulated phases below 96 (3) and 59 (3) K, with different q vectors, similar to the pure Co compound (with modulated phases below 128 and 96 K); however, it maintains the modulated phase below magnetic order [at 22.5 (7) K], resembling the pure Ni compound (which presents magnetic order below 34 K), resulting in an improper modulated magnetic structure. Despite these large-scale structural changes, magnetometry data reveal that the bulk magnetic properties of these solid solutions form a linear continuum between the end members. Notably, doping of the metal site in these solid solutions allows for tuning of bulk magnetic properties, including magnetic ordering temperature, transition temperatures and the nature of nuclear phase transitions, through adjustment of metal ratios.

Facile microwave synthesis of various-shaped magnetite/ reduced graphene oxide heterostructures and their magnetization properties

Heterostructures of magnetite (Fe3O4) nanoparticles and reduced graphene oxide (RGO) sheets are very common composite materials for different applications such as catalysis, energy storage, and biomedicine. Developing methods for the facile control of the size and shape of both freestanding Fe3O4 nanoparticles and those anchored onto RGO sheets is in demand. Herein, we report on the rapid and facile microwave synthesis (MWS) of Fe3O4 nanoparticles and Fe3O4/RGO with various sizes and shapes using the oleylamine (OAm)/oleic acid (OAc) ligand pair. The solvothermal synthesis using microwave irradiation (MWI) resulted in the concurrent conversion of graphene oxide (GO) into RGO and the in-situ formation of various-shaped Fe3O4 on RGO sheets. Freestanding Fe3O4 nanoparticles of various shapes were prepared using MWS for comparison. The morphological, structural, and surface properties of the samples were studied using different characterization techniques. The magnetization properties of the prepared samples were determined using a vibrating sample magnetometer. Various-shaped standalone and RGO-supported Fe3O4 nanoparticles including nanospheres, nanocubes, and nanotriangles were synthesized via MWI at 1000 W for 20 min by changing the ratios of the iron precursor and the OAm/OAc ligand pair. Interestingly, the MWI using OAm/OAc ligand pair of a molar ratio of 3:4 resulted in the in-situ formation of large hexagonal Fe3O4/RGO. The X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) results confirm the crystallinity and spinel structure of the prepared Fe3O4 samples and prove the concurrent conversion of GO into RGO with assemblies of Fe3O4 nanoparticles. The magnetization measurements further emphasized the role of size and shape in affecting the magnetic properties of Fe3O4 and Fe3O4/RGO heterostructures. The results identify the qualities of the prepared samples and prove the MWS as a facile one-pot method for the preparation of Fe3O4 and Fe3O4/RGO heterostructures.