Antiferromagnetic Coupling Research Articles

Competition between magnetic interactions and structural instabilities leading to itinerant frustration in the triangular lattice antiferromagnet LiCrSe2

LiCrSe2 constitutes a recent valuable addition to the ensemble of two-dimensional triangular lattice antiferromagnets. In this work, we present a comprehensive study of the low temperature nuclear and magnetic structure established in this material. Being subject to a strong magnetoelastic coupling, LiCrSe2 was found to undergo a first order structural transition from a trigonal crystal system (Pbar{3}m1) to a monoclinic one (C2/m) at Ts = 30 K. Such restructuring of the lattice is accompanied by a magnetic transition at TN = 30 K. Refinement of the magnetic structure with neutron diffraction data and complementary muon spin rotation analysis reveal the presence of a complex incommensurate magnetic structure with a up-up-down-down arrangement of the chromium moments with ferromagnetic double chains coupled antiferromagnetically. The spin axial vector is also modulated both in direction and modulus, resulting in a spin density wave-like order with periodic suppression of the chromium moment along the chains. This behavior is believed to appear as a result of strong competition between direct exchange antiferromagnetic and superexchange ferromagnetic couplings established between both nearest neighbor and next nearest neighbor Cr3+ ions. We finally conjecture that the resulting magnetic order is stabilized via subtle vacancy/charge order within the lithium layers, potentially causing a mix of two co-existing magnetic phases within the sample.

A Unique Two-Dimensional Silver(II) Antiferromagnet Cu[Ag(SO4 )2 ] and Perspectives for Its Further Modifications.

Copper(II) silver(II) sulfate crystallizes in a monoclinic CuSO4 -related structure with P21 /n symmetry. This quasi-ternary compound features Ag(SO4 )2 2- layers, while the remaining cationic sites may be occupied either completely or partially by Cu2+ cations, corresponding to the formula of (Cux Ag1-x )[Ag(SO4 )2 ], x=0.6-1.0. CuAg(SO4 )2 is antiferromagnetic with large negative Curie-Weiss temperature of -140 K and shows characteristic ordering phenomenon at 40.4 K. Density functional theory calculations reveal that the strongest superexchange interaction is a two-dimensional antiferromagnetic coupling within Ag(SO4 )2 2- layers, with the superexchange constant J2D of -11.1 meV. This renders CuAg(SO4 )2 the rare representative of layered Ag2+ -based antiferromagnets. Magnetic coupling is facilitated by the strong mixing of Ag d(x2 -y2 ) and O 2p states. Calculations show that M2+ sites in MAg(SO4 )2 can be occupied with other similar cations such as Zn2+ , Cd2+ , Ni2+ , Co2+ , and Mg2+ .

Understanding Antiferromagnetic and Ligand Field Effects on Spin Crossover in a Triple-Decker Dimeric Cr(II) Complex.

Two possible explanations for the temperature dependence of spin-crossover (SCO) behavior in the dimeric triple-decker Cr(II) complex ([(η5-C5Me5)Cr(μ2:η5-P5)Cr(η5-C5Me5)]+) have been offered. One invokes variations in antiferromagnetic interactions between the two Cr(II) ions, whereas the other posits the development of a strong ligand-field effect favoring the low-spin ground state. We perform multireference electronic structure calculations based on the multiconfiguration pair-density functional theory to resolve these effects. We find quintet, triplet, and singlet electronic ground states, respectively, for the experimental geometries at high, intermediate, and low temperatures. The ground-state transition from quintet to triplet at an intermediate temperature derives from increased antiferromagnetic interactions between the two Cr(II) ions. By contrast, the ground-state transition from triplet to singlet at low temperature can be attributed to increased ligand-field effects, which dominate with continued variations in antiferromagnetic coupling. This study provides quantitative detail for the degree to which these two effects can act in concert for the observed SCO behavior in this complex and others subject to temperature-dependent variations in geometry.

Electronic and Magnetic Properties of FeCl3 Intercalated Bilayer Graphene

Graphene has gained significant attention since its discovery in 2004, and the modification of few-layer graphene provides a platform to tailor its physical and electronic properties. In this study, we employed unrestricted density functional theory (DFT) with the PBE+U functional to investigate the electronic and magnetic properties of FeCl3-intercalated bilayer graphene (BLG). Both in BLG and stage-2 intercalated graphite, a distinct localization of electrons on a specific Fe atom is evident, gaining approximately 0.245 electrons evaluated with Bader analysis, while the holes are delocalized within the graphene layers. This results in p-doped graphene, characterized by a shift of the Dirac cone by 0.74 eV for BLG and 0.70 eV for stage-2 intercalated graphite. Ferromagnetic ordering is observed within the plane of FeCl3-intercalated BLG, whereas the FeCl3 layers exhibit antiferromagnetic coupling in stage-2 intercalated graphite. The ferromagnetic nature and electronic structure of the FeCl3-intercalated BLG is retained under pressure.

Slow magnetic relaxation behaviors and diamagnetic dilution studies of a carboxyl bridged dinuclear dysprosium(III) complex

By using a rigid bulky carboxylic ligand α-cyanocinnamic acid (CCA), a dinuclear dysprosium (III) complex [Dy2(CCA)6 (MeOH)4] (1) was synthesized. Single crystal X-ray crystallography reveals that the two eight-coordinate dysprosium ions are bridged by four deprotonated carboxyl groups, forming a centrosymmetric paddle-wheel-like structure. Dynamic magnetic property measurements indicate that complex 1 displays field-induced slow magnetic relaxation. The temperature-dependent relaxation times can be fitted using Orbach and Raman processes with parameters of n = 2.8 (2), C = 27 (8) s−1/Kn, τ0 = 5 (2) × 10−10 s and Ueff = 40 (3) cm−1. Magnetic studies on the diamagnetic YIII-diluted analogue [Dy0.206Y1.794(CCA)6 (MeOH)4] (2) reveal its slow magnetic relaxation behavior without external dc field and the antiferromagnetic coupling between the DyIII ions in 1. Fits on the obtained relaxation times of 2 lead to the parameters of n = 4.5 (3), C = 0.7 (2) s−1/Kn, τ0 = 2.8 (2) × 10−9 s and Ueff = 38 (2) cm−1. The results suggest that slow magnetic relaxation originates from the single-ion relaxation of DyIII ions. Moreover, the diamagnetic dilution can suppress other fast relaxation pathways at low temperature, on account of the elimination of magnetic coupling and dipolar interaction. Ab initio calculations were then performed on the single DyIII ion species {YDy} and indicate that the first excited Kramers doublets (KDs) lie at ca. 76 cm−1, which is slightly higher than the experimental Ueff value. The intramolecular magnetic interactions were also calculated and indicate a weak ferromagnetic dipole-diploe magnetic interaction and an antiferromagnetic exchange coupling.

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.

The Stack Optimization of Magnetic Heterojunction Structures for Next-Generation Spintronic Logic Applications.

Magnetic heterojunction structures with a suppressed interfacial Dzyaloshinskii-Moriya interaction and a sustainable long-range interlayer exchange coupling are achieved with an ultrathin platinum insertion layer. The systematic inelastic light scattering spectroscopy measurements indicate that the insertion layer restores the symmetry of the system and, then, the interfacial Dzyaloshinskii-Moriya interaction, which can prevent the identical magnetic domain wall motions, is obviously minimized. Nevertheless, the strong interlayer exchange coupling of the system is maintained. Consequently, synthetic ferromagnetic and antiferromagnetic exchange couplings as a function of the ruthenium layer thickness are observed as well. Therefore, these optimized magnetic multilayer stacks can avoid crucial issues, such as domain wall tilting and position problems, for next-generation spintronic logic applications. Moreover, the synthetic antiferromagnetic coupling can open a new path to develop a radically different NOT gate via current-induced magnetic domain wall motions and inversions.

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.

Binary frequency shift keying modulation in spin torque oscillators with synthetic antiferromagnetic layer

Antiferromagnets exhibit ultrafast magnetization precession, which has the potential to enable the development of terahertz spin torque nano-oscillators. By utilizing perpendicularly magnetized magnetic nanopillars with a synthetic antiferromagnetic (SAF) free layer, we have demonstrated through theoretical and numerical analysis that stable out-of-plane precession states can be achieved by applying current and an electric field. In the case of small current, the two magnetic layers of the SAF are in antiparallel alignment and rotate around the z-axis with the precession frequency decreasing as the current strength increases. When the current-induced spin torque is strong enough to fully overcome the antiferromagnetic coupling, the SAF free layer is driven into a scissor-like precession state around the z-axis with the frequency increasing with current. By selecting the appropriate combination of the current and electric field, the magnetization precession orbits and precession frequencies can be adjusted. These controllable procession orbits with tunable frequencies and fixed magnetization precession amplitude may be a promising candidate for implementing binary frequency shift keying modulation techniques.

Frustrated magnetism of the spin-1 kagome antiferromagnet β-BaNi3(VO4)2(OH)2

We propose the newly synthesized β-BaNi3(VO4)2(OH)2 (space group: ) as a candidate for the spin-1 kagome Heisenberg antiferromagnet (KHA). The compound features a uniform kagome lattice of Ni2+ (S = 1) ions with a large interlayer distance. High-field measurements at low temperatures reveal a susceptibility local minimum at ∼9 T, resembling a 1/3 magnetization plateau as predicted by the pure S = 1 KHA model. Below ∼6 K, approximately 1% of the spins exhibit spin-glass order, which may be attributed to the nanocrystalline grain size of ∼50 nm. Despite the antiferromagnetic exchange coupling strength of ∼7 K, the majority of spins remain disordered down to ∼0.1 K as indicated by the observed power-law behaviors in magnetic specific heat . Our results demonstrate that the low-energy magnetic excitations in β-BaNi3(VO4)2(OH)2 are gapless, which contradicts the current theoretical expectations of the ideal model.

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.

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.

Benzimidazole-diamide (bida) Pincer Chromium Complexes: Structures and Reactivity.

Serendipitous discovery of bida (i.e., N1-Ar-N2-((1-Ar-1-benzo[d]imidazol-2-yl)methyl)benzene-1,2-diamide; Ar = 2,6-iPr-C6H3), a potentially redox noninnocent, hemilabile pincer ligand with a methylene group that may facilitate proton/H atom reactivity, prompted its investigation. Chromium was chosen for study due to its multiple stable oxidation states. Disodium salt (bida)Na2(THF)n was prepared by thermal rearrangement of (dadi)Na2(THF)4 (i.e., (N,N'-di-2-(2,6-diisopropylphenylamine)phenylglyoxaldiimine)-Na2(THF)4). Salt metathesis of (bida)Na2(THF)n (generated in situ) with CrCl3(THF)3 or Cl3V═NAr (Ar = 2,6-iPr2C6H3) afforded (bida)CrCl(THF) (1-THF) and (bida)ClV═NAr, respectively. Substitutions provided (bida)CrCl(PMe2Ph) (1-PMe2Ph) and (bida)CrR(THF) (2-R, where R = Me, CH2CMe2Ph (Nph)). Oxidation of 1-THF with ArN3 (Ar = 2,6-iPr2C6H3) or AdN3 (Ad = 1-adamantyl) generated (bida)ClCr═NAr (3═NAr) and (bida)ClCr═NAd (3═NAd) and subsequent alkylation converted these to (bida)R'Cr═NR (R' = Me, R = Ad, Ar, 5═NR; R' = CH2CMe2Ph (Nph), R = Ad, Ar, 6═NR). In contrast, the addition of AdN3 to 2-Nph gave the insertion product (bida)Cr(κ2-N,N-ArN3Nph) (7). Addition of N-chlorosuccinimide to 1-THF produced (bia)CrCl2(THF) (8), where bia is the pincer derived via hydrogen atom loss from bida methylene. A similar HAT afforded (bia)ClCr(CNAr')2 (9, Ar' = 2,6-Me2C6H3) when 3═NAd was exposed to Ar'NC. An empirical equation of charge was applied to each bida species, whose metric parameters are unchanging despite formal oxidation state conversions from Cr(III) to Cr(V). Calculations and Mulliken spin density assessments reveal several situations in which antiferromagnetic (AF) coupling and admixtures of integer ground states (GSs) describe a complicated electronic structure.

Bi2Te3-intercalated MnBi2Te4: ideal candidate to explore intrinsic Chern insulator and high-temperature quantum anomalous Hall effect

The recently discovered magnetic topological insulator of MnBi2Te4 (MBT), has been demonstrated to realize the quantum anomalous Hall (QAH) effect, while the naturally antiferromagnetic (AFM) interlayer coupling in MBT results in that the QAH effect can only be realized in odd-layered systems and at low temperature. Using first-principles calculations, we find that intercalating Bi2Te3 (BT) layers into MBT by forming MBT/(BT) n /MBT (n = 1–6) heterostructures can induce magnetic phase transition from AFM to ferromagnetic (FM) interlayer coupling when n⩾ 3. Specifically, MBT/(BT)3/MBT and MBT/(BT)4/MBT respectively host Curie temperatures T c of 14 K and 11 K, which fits well the experimentally measured T c of 12 K. Detailed band structure calculations and topological identification show that the QAH phases are well preserved for all FM heterostructures. And the topological mechanism of MBT/(BT) n /MBT as a function of n is revealed by employing continuum model analysis. Most importantly, the FM MBT/(BT)4/MBT has already been experimentally fabricated. Thus, our work provides a practical guideline to explore high-temperature QAH effect in MBT family of materials.

A new layered potassium-based molybdenum–tungsten monophosphate: synthesis, crystal structure, XPS and magnetic studies

Abstract A new compound, K5[(Mo3.2W1.8)O11](PO4)3[(P0.5Mo0.5)O4], was synthesized via solid-state reaction and its crystal structure was determined by single-crystal X-ray diffraction. This compound crystallizes in the space group Pnma, with a = 9.0360(4) Å, b = 10.1603(4) Å, c = 26.1538(12) Å and V = 2401.14(18) Å3. The structure consists of a corner-sharing MO6–TO4 (M = Mo, W; T = P, Mo) polyhedral connection arranged to form an ordered packing of ∼14.9 Å-thick layers parallel to (001). The stacking of the layers forms trigonal, tetragonal and hexagonal channels. XPS study reveals the presence of W at the hexavalent state only, whereas Mo appears as a mixed-valent species (Mo6+, Mo5+ and Mo4+). Magnetic susceptibility reveals the occurrence of a relevant antiferromagnetic coupling and is consistent with the presence of reduced metal species as indicated by the XPS results.

A candidate exchange-biased vdW heterostructure based on Cr2NO2 and Cr2CF2 MXenes

We investigated the van der Waals heterostructure Cr2NO2/Cr2CF2 by spin-polarized first-principles calculations. The aim is to create two-dimensional ferromagnetic/antiferromagnetic heterostructures where the exchange bias effect can occur. Cr2NO2 MXene is a half-metal ferromagnetic material, while Cr2CF2 MXene is an antiferromagnetic semiconductor. The lattice mismatch of both MXenes is ∼4%, good enough to construct the heterostructure. Three different stackings were considered in the heterostructure: H3, T4, and Top. Also, three different cell parameters are considered: larger lattice constant a(Cr2CF2), shorter lattice constant a(Cr2NO2), and both relaxed. In all cases, T4 staking is the most favorable interaction configuration. Non-covalent interactions show that van der Waals forces dominate in the heterostructure. Also, the average electrostatic potential along the z-axis explains the stability in the T4 stacking. Antiferromagnetic coupling is the most stable when fixing a(Cr2CF2) as the heterostructure lattice parameter, while for the short lattice constant, a(Cr2NO2), the magnetic coupling becomes Ferromagnetic. Band diagrams evidence that both MXenes preserve their electronic properties after the interaction, so the antiferromagnetic alignment is intrinsic in the heterostructure for the larger lattice constant. Our theoretical findings open the door to consider the versatile MXenes as promising candidates for the new generation of information storage nanodevices.

Quantum geometric spin frustration of antiferromagnetic CuFeO2 enables photocatalytic applications

Photocatalysis, containing a potential solution to the global crises of energy shortage and the greenhouse effect, has been studied extensively in recent years. The CuFeO2 (abbreviated as CFO) is a material with a Delafossite structure, and has also been widely studied because of its triangular lattice antiferromagnets. The triangular lattice composed of Fe3+ ions, along with strong antiferromagnetic spin coupling between the Fe3+ ions, leads to a geometric spin frustration. Furthermore, CFO is also a potential candidate for the photocatalytic material due to its narrow band gap of 1.1–1.6 eV, electrochemical stability in an aqueous environment, high charge carrier mobility, flat-band potential positioned at ∼ 1 eV, and contains an abundance of raw materials in the earth. In this study, we successfully grew the size and highly-quality CFO single crystals using the optical floating-zone technique. Powder x-ray diffraction (XRD) and Rietveld refinement indicate that the CFO is a rhombohedral structure with a space group of R3̅m, consisting of edge-shared FeO6 octahedron to form the FeO2 layer, and the Cu cations occupied between the two FeO2 layers. The core-level electron energy loss (EEL) spectra found the valence of Fe and Cu in CFO is +3 and +1, respectively. The low-loss EEL spectrum observed two volume plasmons at ∼5 eV and ∼23 eV contributed from the collective oscillation of Cu-O antibonding states σCu−O* and mixed nonbonding Cu 3dxy, σCu−O bonding states, and Fe-O, respectively, based on the density function theory calculation. The optical absorption spectrum measured the energy bandgap for CFO is about 1.5 eV. The Raman spectrum shows significant Eg and A1 g vibration modes corresponding to the in-plane Fe-O and out-of-plane Cu-O vibrations, respectively. Both magnetic susceptibility, χ(T), with the applied magnetic field along the c-axis and specific heat capacity reveal the two magnetic phase transition temperatures at low temperatures: TN1 = 13.5 K when transition from paramagnetic (PM) phase to partially disordered antiferromagnetic, and TN2 = 10.5 K when complete transition from partially disordered antiferromagnetic to antiferromagnetic phase. The additional calculation of magnetic entropy change is 0.15, which is roughly close to 0.2, meaning that only 1/5 of the Fe3+ spins are disordered when transforming from PM states to partially disordered at T < TN1 in this study. The presence of instantaneous ferromagnetic spin arrangement (↑↑↓) extends the residence time of H2O on the surface of CFO, facilitating electron exchange with CFO and promoting photocatalytic water splitting reactions.

Magneto-structural studies on [CuII2{L3-(μ2-1,1-CO2–)2}2]•MeOH•H2O and [CuII4{L4-(μ2-1,3-CO2–)(μ2-1,3-CO2Me)}4](ClO4)4 using carboxylate- / carboxymethylester-appended (2-pyridyl)-alkylamine ligands differing in alkyl chain length

Two discrete complexes [CuII2{L3-(CO2–)2}2]•MeOH•H2O (1) and [CuII4{L4-(CO2–)(CO2Me)}4](ClO4)4•unknown solvent (2) have been synthesized from the reaction between copper(II) salts and L3-(CO2Me)2 / L4-(CO2Me)2 [3,3′-[(pyridin-2-ylmethyl)imino]dipropionate dimethylester / 3,3′-[(pyridin-2-ylethyl)imino]dipropionate dimethylester]. Structural analysis reveals that 1 is a monatomic bridging carboxylate dinuclear complex with CuII2(μ2-1,1-OCO–)22+ structural unit. Each Cu(II) centre has distorted square-pyramidal CuN2O3 coordination, provided by two N (pyridyl and amine) and two carboxylate O from L3-(CO2–)2 and the fifth coordination is provided by an O atom belonging to the carboxylate group of an adjacent molecule. Complex 2 is a syn-anti carboxylate-bridged tetranuclear coordination cluster with a {CuII4{(μ2-1,3-OCO–)(μ2-1,3-OCOMe)}44+ structural motif. Here also, each Cu(II) centre has distorted square-pyramidal CuN2O3 coordination, and an O atom belonging to the carboxylate group of an adjacent molecule completes the fifth coordination. Variable temperature magnetic studies reveal antiferromagnetic coupling in 1 (J = –8.37(6) cm−1), while 2 exhibits ferromagnetic behaviour (J = +13.1(1) cm−1).

Ligand Control of Dinitrosyl Iron Complexes for Selective Superoxide-Mediated Nitric Oxide Monooxygenation and Superoxide-Dioxygen Interconversion.

Through nitrosylation of [Fe-S] proteins, or the chelatable iron pool, a dinitrosyl iron unit (DNIU) [Fe(NO)2] embedded in the form of low-molecular-weight/protein-bound dinitrosyl iron complexes (DNICs) was discovered as a metallocofactor assembled under inflammatory conditions with elevated levels of nitric oxide (NO) and superoxide (O2-). In an attempt to gain biomimetic insights into the unexplored transformations of the DNIU under inflammation, we investigated the reactivity toward O2- by a series of DNICs [(NO)2Fe(μ-MePyr)2Fe(NO)2] (1) and [(NO)2Fe(μ-SEt)2Fe(NO)2] (3). During the superoxide-induced conversion of DNIC 1 into DNIC [(K-18-crown-6-ether)2(NO2)][Fe(μ-MePyr)4(μ-O)2(Fe(NO)2)4] (2-K-crown) and a [Fe3+(MePyr)x(NO2)y(O)z]n adduct, stoichiometric NO monooxygenation yielding NO2- occurs without the transient formation of peroxynitrite-derived •OH/•NO2 species. To study the isoelectronic reaction of O2(g) and one-electron-reduced DNIC 1, a DNIC featuring an electronically localized {Fe(NO)2}9-{Fe(NO)2}10 electronic structure, [K-18-crown-6-ether][(NO)2Fe(μ-MePyr)2Fe(NO)2] (1-red), was successfully synthesized and characterized. Oxygenation of DNIC 1-red leads to the similar assembly of DNIC 2-K-crown, of which the electronic structure is best described as paramagnetic with weak antiferromagnetic coupling among the four S = 1/2 {FeIII(NO-)2}9 units and S = 5/2 Fe3+ center. In contrast to DNICs 1 and 1-red, DNICs 3 and [K-18-crown-6-ether][(NO)2Fe(μ-SEt)2Fe(NO)2] (3-red) display a reversible equilibrium of "3 + O2- ⇋ 3-red + O2(g)", which is ascribed to the covalent [Fe(μ-SEt)2Fe] core and redox-active [Fe(NO)2] unit. Based on this study, the supporting/bridging ligands in dinuclear DNIC 1/3 (or 1-red/3-red) control the selective monooxygenation of NO and redox interconversion between O2- and O2 during reaction with O2- (or O2).

Coexistence of antiferromagnetism and unconventional superconductivity in a quasi-one-dimensional flat-band system: Creutz lattice

We study the coexistence of antiferromagnetism and unconventional superconductivity on the Creutz lattice which shows strictly flat bands in the noninteracting regime. The famous renormalized mean-field theory is used to deal with strong electron–electron repulsive Hubbard interaction in the effective low-energy t–J model, the superfluid weight of the unconventional superconducting state has been calculated via the linear response theory. An unconventional superconducting state with both spin-singlet and staggered spin-triplet pairs emerges beyond a critical antiferromagnetic coupling interaction, while antiferromagnetism accompanies this state. The superconducting state with only spin-singlet pairs is dominant with paramagnetic phase. The A phase is analogous to the pseudogap phase, which shows that electrons go to form pairs but do not cause a supercurrent. We also show the superfluid behavior of the unconventional superconducting state and its critical temperature. It is proven directly that the flat band can effectively raise the critical temperature of superconductivity. It is implementable to simulate and control strongly-correlated electrons’ behavior on the Creutz lattice in the ultracold atoms experiment or other artificial structures. Our results may help the understanding of the interplay between unconventional superconductivity and magnetism.