Strong Antiferromagnetic Coupling Research Articles

Enhancement of interlayer exchange coupling via intercalation in 2D magnetic bilayers: towards high Curie temperature.

Two-dimensional magnetic materials are considered as promising candidates for developing next-generation spintronic devices by providing the possibility of scaling down to nanometers. However, a low Curie temperature is a crucial problem for practical applications, being intimately related to weak interlayer exchange coupling. Here, by using density functional theory calculations, we show that interlayer exchange coupling can be enhanced by intercalating 3d transition metals (Sc to Zn) into a bilayer of CrI3 and NiI2. It is found that intercalated Ni and Cr atoms exhibit strong antiferromagnetic coupling with the CrI3 and NiI2 host layers, respectively. This enhances the ferromagnetic interlayer exchange coupling between the host layers by many folds compared to pristine CrI3 and NiI2 bilayers. Moreover, both intercalated compounds show out-of-plane magnetic anisotropy with half metallic nature, which makes them ideal candidates for spintronics applications. Thereby our work provides a rational approach to raise the Curie temperature of non-metallic two-dimensional magnets by intercalation.

Cryogenic magnetocaloric effects of NaLnF4 (Ln = Gd, Tb, Dy, Ho, Er, Tm, and Yb)

Cryogenic refrigeration technology based on magnetocaloric effects plays a critical role in a variety of technological applications. In this paper, we report the cryogenic magnetocaloric effects of a series of sodium-rare earth fluoride samples (Ln = Gd, Tb, Dy, Ho, Er, Tm, Yb) synthesized by the solid-state reaction method. These compounds all crystallize in a hexagonal crystal structure. Down to 2 K, no magnetic ordering was detected, while all compounds show negative Curie–Weiss temperatures indicative of strong antiferromagnetic coupling. Magnetic fields effectively suppress the magnetic fluctuations, leading to a maximum magnetic entropy change of −56 J kg−1 K−1 in NaGdF4 at the magnetic field change from 0 to 50 kOe. These series of compounds are potentially excellent magnetic refrigerants at low temperatures.

Geometrically frustrated Gd2Ti2O7 oxide: A comprehensive exploration of structural, magnetic, and magnetocaloric properties for cryogenic magnetic cooling applications

The magnetocaloric effect (MCE) has been extensively studied in various magnetic solids, aiming to both facilitate practical applications in magnetic cooling and deepen our understanding these materials’ intrinsic properties. This study presents a systematic investigation of Gd2Ti2O7 oxide, characterized by a geometrically frustrated magnetic structure, focusing on its structural and magnetic characteristics through experimental analysis and theoretical calculations. Emphasis is placed on its magnetic phase transition (MPT) and magnetocaloric properties, scrutinizing temperatures as low as 0.4 K and magnetic fields up to 16 T. The results reveal that Gd2Ti2O7 oxide possesses a crystalline cubic pyrochlore-type structure with an antiferromagnetic (AFM) semiconductor ground state. The material undergoes a first-order MPT in low field and low-temperature regimes, transitioning to a second-order MPT above 2 K up to 16 T. Evaluation of magnetocaloric parameters, including maximum magnetic entropy change, temperature-averaged entropy change, relative cooling power, and refrigerant capacity, indicates moderate values under low magnetic field changes, while significantly large values are achievable under high magnetic field changes. This finding suggests that potential cryogenic magnetocaloric materials (MCMs) with optimal performance should exhibit low MPT temperatures induced by magnetic frustration and possess a ground state with a sufficiently large magnetic moment induced by low magnetic fields, thus avoiding excessively strong AFM coupling. This study lays the groundwork for future cryogenic MCM design and provides valuable insights into the intrinsic properties of geometrically frustrated magnetic materials.

Unusual Stabilisation of Remarkably Bent Tetra-Cationic Tetra-radical Intermolecular Fe(III) μ-Oxo Tetranuclear Complexes.

A hitherto unknown series of air stable, π-conjugated, remarkably bent tetra-cation tetra-radical intermolecular Fe(III) μ-oxo tetranuclear complex, isolated from the dication diradical diiron(III) porphyrin dimers, has been synthesised and spectroscopically characterised along with single crystal X-ray structure determination of two such molecules. These species facilitate long-range charge/radical delocalisation through the bridge across the entire tetranuclear unit manifesting an unusually intense NIR band. Assorted spin states of Fe(III) centres are stabilised within these unique tetranuclear frameworks: terminal six-coordinate iron centres stabilise the admixed intermediate spin states while the central five-coordinate iron centres stabilise the high-spin states. Variable temperature magnetic susceptibility measurements indicated strong antiferromagnetic coupling for the Fe(III)-O-Fe(III) unit while the exchange interactions between the Fe centres and the porphyrin π-cation radicals are weaker as supported both by magnetic data and DFT calculations. The nature of orbital overlap between the SOMOs of Fe(III) and π* orbital of the porphyrin was found to rationalise the observed exchange coupling, establishing such a complex magnetic exchange in this tetranuclear model with a significant bioinorganic relevance.

Unusual Stabilisation of Remarkably Bent Tetra‐Cationic Tetra‐radical Intermolecular Fe(III) μ‐Oxo Tetranuclear Complexes

AbstractA hitherto unknown series of air stable, π‐conjugated, remarkably bent tetra‐cation tetra‐radical intermolecular Fe(III) μ‐oxo tetranuclear complex, isolated from the dication diradical diiron(III) porphyrin dimers, has been synthesised and spectroscopically characterised along with single crystal X‐ray structure determination of two such molecules. These species facilitate long‐range charge/radical delocalisation through the bridge across the entire tetranuclear unit manifesting an unusually intense NIR band. Assorted spin states of Fe(III) centres are stabilised within these unique tetranuclear frameworks: terminal six‐coordinate iron centres stabilise the admixed intermediate spin states while the central five‐coordinate iron centres stabilise the high‐spin states. Variable temperature magnetic susceptibility measurements indicated strong antiferromagnetic coupling for the Fe(III)−O−Fe(III) unit while the exchange interactions between the Fe centres and the porphyrin π‐cation radicals are weaker as supported both by magnetic data and DFT calculations. The nature of orbital overlap between the SOMOs of Fe(III) and π* orbital of the porphyrin was found to rationalise the observed exchange coupling, establishing such a complex magnetic exchange in this tetranuclear model with a significant bioinorganic relevance.

Alkoxy-Bridged Dicopper(II) Cores Meet Tetracyanonickelate Linkers: Structural, Magnetic, and Theoretical Investigation of Cu/Ni Coordination Polymers.

Two heterometallic Cu(II)/Ni(II) coordination polymers, [Cu2(Hbdea)2Ni(CN)4]n (1) and [Cu2(dmea)2Ni(CN)4]n·nH2O (2), were successfully self-assembled in water by reacting Cu(II) nitrate with H2bdea (N-butyldiethanolamine) and Hdmea (N,N-dimethylethanolamine) in the presence of sodium hydroxide and [Ni(CN)4]2-. These new coordination polymers were investigated by single-crystal and powder X-ray diffraction and fully characterized by FT-IR spectroscopy, thermogravimetry, elemental analysis, variable-temperature magnetic susceptibility measurements, and theoretical DFT and CASSCF calculations. Despite differences in crystal systems, in both compounds, each dinuclear building block [Cu2(μ-aminopolyalcoholate)2]2+ is bridged by diamagnetic [Ni(CN)4]2- linkers, resulting in 1D (1) or 2D (2) metal-organic architectures. Experimental magnetic studies show that both compounds display strong antiferromagnetic coupling (J = -602.1 cm-1 for 1 and -151 cm-1 for 2) between Cu(II) ions within the dimers mediated by the μ-O-alkoxo bridges. These results are corroborated by the broken symmetry DFT studies, which also provide further insight into the electronic structures of copper dimeric units. By reporting a facile self-assembly synthetic protocol, this study can be a model to widen a still limited family of heterometallic Cu/Ni coordination polymer materials with different functional properties.

Investigation of possible spin frustration in isolated isosceles MnIIINiII2 Triangle: Experimental and theoretical studies

Spin frustration is a unique phenomenon in magnetic complexes, where if a spin fails to lower the total energy of the system, by orienting itself in relative to its adjacent spins, it is termed as frustrated. In this work, we discuss about the magnetic properties, and the possibility of spin frustration in our isolated [NiII2MnIII(hep)4(PhCO2)(N3)2] (Hhep = 2-(2-hydroxyethyl) pyridine) having an isosceles NiII2MnIII triangle. The triangular MnIIINiII2 core was held together by two μ3-alkoxide bridges. The magnetic properties of this complex were studied in detail. Variable temperature magnetic susceptibility data of the complex in the range of 1.8 to 300 K, indicates the presence of stronger intramolecular antiferromagnetic coupling between two NiII centres than between NiII and MnIII ions. Experimentally, the ground state of the complex was found to be a mixture of E(2,0) and E(1,1) states, suggesting our complex to be close to a spin frustrated system which was supported by ab initio calculations.

Room-Temperature Entanglement of the Nickel-Radical Molecular Complex (Et3NH)[Ni(hfac)2L] Reinforced by the Magnetic Field

Bipartite entanglement is comprehensively investigated in the mononuclear molecular complex (Et3NH)[Ni(hfac)2L], where HL denotes 2-(2-hydroxy-3-methoxy-5-nitrophenyl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazol-3-oxide-1-oxyl and hfacH stands for hexafluoroacetylacetone. From the magnetic point of view, the molecular compound (Et3NH)[Ni(hfac)2L] consists of an exchange-coupled spin-1 Ni2+ magnetic ion and a spin-12 nitronyl-nitroxide radical substituted nitrophenol. The nickel-radical molecular complex affords an experimental realization of a mixed spin-(12, 1) Heisenberg dimer with a strong antiferromagnetic exchange coupling, J/kB = 505 K, and two distinct g-factors, gRad = 2.005 and gNi = 2.275. By adopting this set of magnetic parameters, we demonstrate that the Zeeman splitting of a quantum ferrimagnetic ground-state doublet due to a weak magnetic field may substantially reinforce the strength of bipartite entanglement at low temperatures. The molecular compound (Et3NH)[Ni(hfac)2L] maintains sufficiently strong thermal entanglement, even at room temperature, vanishing only above 546 K. Specifically, the thermal entanglement in the nickel-radical molecular complex retains approximately 40% of the maximum value, corresponding to perfectly entangled Bell states at room temperature, which implies that this magnetic compound provides a suitable platform of a molecular qubit with potential implications for room-temperature quantum computation and quantum information processing.

Magnetic anisotropy, magnetization reversal and switching in Ni4Nb2O9 single crystals

Ni4Nb2O9 is an insulating compensated ferrimagnet with TN = 77 K and T comp= 33 K. We report here the study of the magnetic anisotropy using millimeter-size crystals grown in an image furnace. The magnetization measurements, vs temperature, performed with H aligned along the three main crystallographic axes, show similar Curie–Weiss temperatures (Θp ≈ 190 K) and rather similar effective paramagnetic moments (from 3.5 μ B to 3.6 μ B). This suggests that the strongest magnetic interaction is the antiferromagnetic one, coupling the ferromagnetic distorted honeycomb layers and zigzag ribbons via face sharing NiO6 octahedra. This strong antiferromagnetic coupling is supported by DFT calculations that do not evidence any inter site ferromagnetic interaction, leading to total compensation between magnetic moments of both Ni2+ sites. Measurements vs magnetic field below TN reveal an anisotropic behaviour, with square magnetization loops for H in the ab plane, whereas linear M(H) curves without hysteresis are observed for H‖c. This anisotropy between ab plane and c axis occurs also in the magnetization reversal (MR), which is observed in the ab plane only. Starting from M(H) virgin curves collected just below T comp= 33 K with H‖a or H‖b, the memory-like effect was tested through magnetization switching induced by H or T alternating changes. Below T comp, smaller H is needed to switch M symmetrically for H along b than along a, and, for T switching (2 K interval, constant H), a larger M change is obtained along a than along b. The comparison with ferrimagnetic oxides which exhibit MR, like spinels or rare earth orthoferrites, shows that Ni4Nb2O9 is unique since only one magnetic cation over two sites in octahedral coordination is at play, thus providing a unique platform to study M switching but also a challenge for theoretical interpretation.

Antiaromatic Molecules as Magnetic Couplers: A Computational Quest.

In this study, we investigate a set of organic diradical structures in which two oxo-verdazyl radicals are selected as radical spin centers that are connected (coupled) via six coupler molecules (CM), resulting in various magnetic (ferromagnetic (FM) or antiferromagnetic (AFM)) characteristics, as reflected by their exchange coupling constants (J). We have designed 12 diradicals with 6-antiaromatic couplers coupled with bis-oxo-verdazyl diradicals with meta-meta (m-m) and para-meta (p-m) positional connectivities. The nature of the magnetic coupling (ferromagnetic, nonmagnetic, or antiferromagnetic) and the magnitude of the exchange constant J depend on the type of coupler, the connecting point between each radical center and CM, the degree of aromaticity of the coupler, and the length of the through-bond distance between radical centers. The computed magnetic exchange coupling constants J for these diradicals at the B3LYP/6-311++G(d,p) and MN12SX/6-311++G(d,p) levels of theory are large for many of these structures, indicating strong ferromagnetic coupling (with positive J values). In some cases, magnetic couplings are observed with J > 1000 cm-1 (B3LYP/6-311++G(d,p)) and strong antiferromagnetic coupling (with negative J values) with J < -1000 cm-1 (B3LYP/6-311++G(d,p)). Similarly, in some cases, magnetic couplings are observed with J > 289 cm-1 (MN12SX/6-311++G(d,p)) and strong antiferromagnetic coupling (with negative J values) with J < -568 cm-1 (MN12SX/6-311++G(d,p)). Furthermore, while numerous studies have reported that the degree of aromaticity of molecular couplers often favors strong ferromagnetic coupling, displaying the high-spin character of diradicals in their ground states, the couplers chosen in this study are characterized as antiaromatic or nonaromatic. The current investigation provides evidence that, remarkably, antiaromatic couplers are able to enhance stability by favoring electronic diradical structures with very strong ferromagnetic coupling when the length of the through-bond distance and connectivity pattern between radical centers are selected in such a way that the FM coupling is optimized. The findings in this study offer new strategies in the design of novel organic materials with interesting magnetic properties for practical applications.

Dinitrogen Activation Mediated by the (P2PPh)Fe Complex: Electronic Structure, Dimerization Mechanism, and Magnetic Coupling.

Herein, we report the estimation of the extent of dinitrogen activation by different charged and structural forms of (P2PPh)Fe biomimetic catalysts, which, in the presence of light, exhibit significant yield in the N2-to-NH3 conversion. Complete active space self-consistent field (CASSCF) calculations have been used to determine the electronic structure of different reduced forms of the mononuclear complexes: the neutral (P2PPh)Fe(N2)2 adduct and the anionic [(P2PPh)Fe(N2)]- and [(P2PPh)Fe(N2)]2- complexes. These calculations also revealed that the extent of reduction of a dinitrogen molecule reaches up to one electron (N21-) due to the back-bonding from the Fe center, in agreement with the changes observed in the vibration frequency of the N-N bond in these complexes. In addition, the energy profile of the dimerization of the mononuclear (P2PPh)Fe(N2)2 complex to the dinuclear mono-N2-bridged [(P2PPh)Fe]2(μ-N2) complex has been determined by means of density functional theory (DFT) calculations. A three-step mechanism has been proposed for the dimerization, favored by both kinetics and thermodynamics criteria. Finally, the magnetic coupling constant in the diiron (μ-N2) complex is estimated from CASSCF/NEVPT2 calculations. Such a dinuclear complex presents a strong antiferromagnetic coupling resulting from the interaction between two S = 1 d6 Fe2+ ions, bridged by a highly activated dinitrogen molecule (N22-) with two electrons on the π* orbitals.

Tuning the magnetic coupling between manganese porphyrins in the 2MnIITPP⋅L assemblies, where L is 6,13-pentacenequinone, isoviolanthrone2− and {MnII(triazole−)2Pc}2−. Key role of a linker (L) in magnetic exchange

Coordination architectures involving high-spin S = 5/2 manganese (II) tetraphenylporphyrins (MnIITPP) and a series of π-conjugated linkers have been obtained. Different molecules (isoviolanthrone, 6,13-pentacenequinone, 1,2,4-triazole anions coordinated to manganese (II) phthalocyanine [(MnII(triazole−)2Pc)]2−) in either dianion or neutral states were used as linkers in these architectures. Complexes [cryptand(K+)]2⋅[(isoviolanthrone2−)⋅{MnIITPP}2]2−⋅5C6H4Cl2 (1) and [(6,13-pentacenequinone0)⋅{MnIITPP}2]0⋅2C6H4Cl2 (2) are formed as a result of the reaction of MnIITPP with isoviolanthrone2− or MnIIIClTPP with 6,13-pentacenequinone2−. Rather weak magnetic coupling between MnII atoms is due to their large spatial separation by diamagnetic isoviolanthrone2− or pentacenequinone0 linkers. Two MnIITPP units are bridged by a paramagnetic [(MnII(triazole−)2Pc)]2− dianion linker with low-spin S = 1/2 manganese(II) atoms within Pc in [cryptand(Na+)]2⋅[(MnII(triazole−)2Pc)⋅{MnIITPP}2]2−⋅5C6H4Cl2 (3). As a result, a triple-decker homotrimetallic [(MnII(triazole−)2Pc)⋅{MnIITPP}2]2− anionic assembly is formed with three paramagnetic nuclei having S = 1/2 and 5/2 spin states, respectively. Strong antiferromagnetic coupling between high-spin outer MnIITPP and low-spin central MnIIPc units is observed in 3 with J = - 35.2 cm−1. Such coupling induces a parallel alignment of outer S = 5/2 spins antiparallel to the central S = 1/2 spin yielding the high-spin S = 9/2 state at 2 K. X-ray crystallography, spectral, magnetic susceptibility data, and EPR are in line with these assignments.

Generation, Spectroscopic Characterization, and Computational Analysis of a Six-Coordinate Cobalt(III)-Imidyl Complex with an Unusual S = 3/2 Ground State that Promotes N-Group and Hydrogen Atom-Transfer Reactions with Exogenous Substrates.

We report the synthesis and characterization of a mononuclear nonheme cobalt(III)-imidyl complex, [Co(NTs)(TQA)(OTf)]+ (1), with an S = 3/2 spin state that is capable of facilitating exogenous substrate modifications. Complex 1 was generated from the reaction of CoII(TQA)(OTf)2 with PhINTs at -20 °C. A flow setup with ESI-MS detection was used to explore the kinetics of the formation, stability, and degradation pathway of 1 in solution by treating the Co(II) precursor with PhINTs. Co K-edge XAS data revealed a distinct shift in the Co K-edge compared to the Co(II) precursor, in agreement with the formation of a Co(III) intermediate. The unusual S = 3/2 spin state was proposed based on EPR, DFT, and CASSCF calculations and Co Kβ XES results. Co K-edge XAS and IR photodissociation (IRPD) spectroscopies demonstrate that 1 is a six-coordinate species, and IRPD and resonance Raman spectroscopies are consistent with 1 being exclusively the isomer with the NT ligand occupying the vacant site trans to the TQA aliphatic amine nitrogen atom. Electronic structure calculations (broken symmetry DFT and CASSCF/NEVPT2) demonstrate an S = 3/2 oxidation state resulting from the strong antiferromagnetic coupling of an •NTs spin to the high-spin S = 2 Co(III) center. Reactivity studies of 1 with PPh3 derivatives revealed its electrophilic characteristic in the nitrene-transfer reaction. While the activation of C-H bonds by 1 was proved to be kinetically challenging, 1 could oxidize weak O-H and N-H bonds. Complex 1 is, therefore, a rare example of a Co(III)-imidyl complex capable of exogenous substrate transformations.

Crystal structure, magnetic and Mössbauer studies of DyFexMn1-xO3 multiferroic manganites

The influence of iron replacement on the structural and magnetic properties of Dysprosium manganites was studied using the series of DyFexMn1-xO3 (x = 0.0, 0.1, 0.3, 0.5, 0.7, 0.9, and 1.0) compounds. All samples were fabricated by means of the modified auto-combustion sol-gel method, followed by the ball milling technique. Orthorhombic structure (Pnma space group) with high phase purity and crystallinity featured all samples, according to X-ray diffraction analysis. The temperature dependence of magnetization curves indicated antiferromagnetic (AFM) to paramagnetic (PM) transition with the increase in temperature. The Néel temperature (TN) was observed to shift to higher temperatures, whereas the spin reorientation transition temperature (TSR) reduced as Fe3+ content increased. Cusps in the zero-field-cooled (ZFC) curves were detected at low temperatures (around 4 K) as an indication of the ordering of the Dy spin. 57Fe Mӧssbauer spectra in samples with low iron content were dominated by a high spin (Fe3+) paramagnetic doublet at both 295 K and 78 K, while the distribution in the hyperfine magnetic field accounted for the appearance of the broadening magnetic peaks. High iron samples revealed a magnetic sextet with fit-resolved patterns that indicated a strong AFM coupling of Fe3+ ions. The hyperfine magnetic field (Bhf) magnitude demonstrated a linear increase with the increase in iron doping.

High Efficiency and Flexible Modulation of Spintronic Terahertz Emitters in Synthetic Antiferromagnets.

Spintronic terahertz (THz) emitters based on synthetic antiferromagnets (SAFs) of FM1/Ru/FM2 (FM: ferromagnet) have shown great potential for achieving coherent superposition and significant THz power enhancement due to antiparallel magnetization alignment. However, key issues regarding the effects of interlayer exchange coupling and net magnetization on THz emissions remain unclear, which will inevitably hinder the performance improvement and practical application of THz devices. In this work, we have investigated the femtosecond laser-induced THz emission in Pt (3)/CoFe (3)/Ru (tRu = 0-3.5)/CoFe (tCoFe = 1.5-10)/Pt (3) (in units of nm) films with compensated and uncompensated magnetic moments. Antiferromagnetic (AF) coupling occurs in the Ru thickness ranges of 0.2-1.1 and 1.9-2.3 nm, with the first peak (tRu = 0.4 nm) of the AF coupling field (Hex) significantly higher than that of the second peak (2.0 nm). Rather high THz amplitude is found for the samples with strong AF coupling. Nevertheless, despite the same remanence ratio of zero, the THz amplitude for the symmetric SAF films declines significantly as the tRu decreases from 0.8 to 0.4 nm, which is mainly ascribed to the noncolinear magnetization vectors due to the increased biquadratic coupling term. Specifically, we demonstrate that an asymmetric SAF structure with a dominant FM layer is more favored than the completely compensated one, which could generate significantly enhanced THz electric field with well-controlled polarity and intensity. In addition, as the temperature decreases, the THz emission intensity increases for the SAF samples of tRu = 0.9 nm with negligible biquadratic coupling, which is contrary to the decreasing trend of the tRu = 0.4 nm sample and has been attributed to the greatly enhanced Hex.

Synthesis, Structural Versatility, Magnetic Properties, and I- Adsorption in a Series of Cobalt(II) Metal-Organic Frameworks with a Charge-Neutral Aliphatic (O,O)-Donor Bridge.

Four new metal-organic frameworks based on cobalt(II) salts and 1,4-diazabicyclo[2.2.2]octane N,N'-dioxide (odabco) were obtained. Their crystallographic formulae are [Co3(odabco)2(OAc)6] (1, OAc- = acetate), [Co(H2O)2(HCOO)2]·odabco (2), [Co2(H2O)(NO3)(odabco)5](NO3)3·3.65H2O (3), and [Co2(DMF)2(odabco)4](NO3)4·3H2O (4; DMF = N,N-dimethylformamide). Crystal structures of 1-4 were determined by single-crystal X-ray crystallography. Coordination polymer 1 comprises binuclear and mononuclear metal-acetate blocks alternating within uncharged one-dimensional chains, in which odabco acts as a bridging ligand. A layered Co(II) formate 2 contains odabco only as guest molecules located in the interlayer space. Layered compound 3 and three-dimensional 4 have cationic coordination frameworks with 26% and 34% specific void volumes, respectively, unveiling high structural diversity of Co(II)-odabco MOFs based on quite a rare aliphatic moiety. Magnetization measurements were performed for 1, 3, and 4 and the obtained data were interpreted on the basis of their crystal structures. A strong (J/kB~100 K) antiferromagnetic coupling was found within binuclear metal blocks in 1. Ion exchange experiments revealed a considerable iodide uptake by 3 resulting in an up to 75% guest nitrate substitution within the voids of a coordination framework, found by capillary zone electrophoresis data and confirmed by single-crystal XRD. A preservation of 3 crystallinity during the exchange allowed for the guest I- positions within a new adduct with the formula [Co2(H2O)(NO3)(odabco)5]I2(NO3)·1.85H2O (3-I) to be successfully determined and the odabco aliphatic core to be revealed as a main adsorption center for quite large and easily polarizable iodide anions. In summary, this work presents a comprehensive study for a series of 1,4-diazabicyclo[2.2.2]octane N,N'-dioxide-based MOFs of cobalt(II) within the framework of magnetic properties and reports the first example of anion exchange in odabco-based coordination networks, supported by direct X-ray structural data. The reported results unveil promising applications of such frameworks bearing ligands with an aliphatic core in the diverse structural design of selective adsorbents and other types of functional materials.

Study of low-dimensional magnetism in zeolitic imidazolate frameworks

Applying the procedure of a rapid synthesis in the aqueous system, nanocrystalline form of ZIF-8 and Cu-ZIF was obtained. The composition of the latter was inferred from the comparison of vibration spectra and lattice specific heats of both compounds which become nearly identical. The nanocrystalline character of both compounds prevented direct comparison of powder XRD patterns and manifested by the appearance of a boson peak in the diamagnetic ZIF-8 specific heat. The low-temperature magnetic contribution in Cu-ZIF specific heat and a Curie-Weiss tail in low-temperature susceptibility may originate from the effect of surface spins while the round maximum observed in the susceptibility at 135 K indicates the presence of strong low-dimensional correlations with the exchange coupling ∼200 K. Corresponding magnetic contribution cannot be observed in the specific heat due to the huge overlap by the high-temperature lattice contribution. Negligible magnetization values at low temperatures correspond to the aforementioned strong antiferromagnetic coupling. Future experimental scenarios are discussed which should provide better understanding of the bulk and surface magnetism in this unique quantum system.

Channeling the exchanges of eg electrons by Co-implantation for magnetism enhancement in CrI3 monolayer

In recent few years, the two-dimensional (2D) magnets have emerged as one of the most important frontiers in materials physics and attracted much attention. As one of the earliest experimentally discovered 2D magnets, CrI3 shows a wealth of properties and has been extensively studied. In particular, an intriguing characteristic of the CrI3 monolayer is its octahedrally coordinated hollow within the unit-cell, which enables the implantation of a magnetic atom, thereby resulting in an artificial 2D superlattice with fertile physics to explore. In this work, using first-principles calculations, we investigate the Co-implanted CrI3 monolayer, denoted as Co-(CrI3)2, and demonstrate the vital roles of the exchange channels of eg electrons in enhancing magnetism. It is shown that the Co-(CrI3)2 monolayer has a half-metallic ferrimagnetic (FiM) ground-state with a net in-plane magnetic moment of 5.0μB/f.u. and a relatively high Curie point (TC) of ∼195 K, noting that TC of pristine CrI3 is only 45–61 K. The FiM ordering is established by the strong anti-ferromagnetic coupling in the t2g-eg exchange channels of the nearest-neighbor (NN) Cr–Co pair and the sizeable ferromagnetic coupling of the third NN Cr–Cr pair mediated by the itinerant eg electrons. In addition, an in-plane biaxial tensile strain of ∼2% may further enhance TC up to ∼210 K. This work offers unique insights into the magnetism enhancement of the CrI3 monolayer by atom-implantation, paving the way for the development of 2D magnets.

Electric field control of the ferromagnetic resonance linewidth in synthetic antiferromagnetic heterostructure

In this study, we present a novel approach to control the microwave properties of a Co/Ru/FeNi film, characterized by strong antiferromagnetic coupling and in plane uniaxial anisotropy. The film is fabricated on a Pb(Mg1/3Nb2/3)O3-PbTiO3 (PMN-PT) ferroelectric substrate using the magnetron oblique sputtering. Our experimental results demonstrate a remarkable non-volatile mediation of the ferromagnetic resonance (FMR) field and linewidth by applying the perpendicular-bias electric field. The observed asymmetric butterfly curve indicates the existence of electric mediation dominated by strain effect. Moreover, we investigate the angular dependence of FMR under different electric field, which reveals changes in magnetic anisotropy including FMR field. Notably, the FMR linewidth exhibits a distinctive four-fold anisotropy. Through microstructure analysis of the film surface, we identify that the origin of this FMR linewidth anisotropy is attributed to the two-magnon scattering induced by the oblique sputtering.

Chiral Ruthenium Halide Semiconductor with Strong Antiferromagnetic Coupling

AbstractChiral hybrid organic–inorganic metal halides have attracted wide attention owing to their superior chiroptoelectronic and chirospintronic properties. Here, a new class of chiral lead‐free metal halides, (R/S‐MBA)3Ru2Br9 (MBA = methylbenzylammonium), with unique magnetic properties is reported. (R/S‐MBA)3Ru2Br9 is composed of a surface‐shared octahedron dimer separated by chiral cations and crystallizes into the Sohncke space group of P212121. The crystal structures, chiroptical, magnetic properties, and magnetic circular dichroism of (R/S‐MBA)3Ru2Br9 are systematically investigated. Owing to the strong antiferromagnetic coupling between the Ru atom through bromine bridge in the [Ru2Br9]3− dimer and the weak ferromagnetic coupling between the neighboring [Ru2Br9]3− dimer, (R/S‐MBA)3Ru2Br9 exhibits antiferromagnetic property with Néel temperature at 7 K. Considering the unique magnetic property of ruthenium, together with the rapid progress of antiferromagnetic spintronics and optospintronics recently, this work provides a novel multifunctional lead‐free chiral magnetic candidate toward chiral optoelectronics and antiferromagnetic spintronics.