Easy-plane Magnetic Anisotropy Research Articles

Investigations of magnetic and thermal expansion properties of two cobalt(II) metal-organic frameworks constructed by mixed bipyridyl-tetracarboxylate strategy

We report the syntheses, crystal structures, adsorption behavior, thermal expansion behavior, and magnetic properties of two cobalt(II) metal-organic frameworks (MOFs), {[Co(btca)1/2(bpe)(H2O)2]·bpe}n (1) and {Co(btca)1/2(bpe)(DMF)}n (2, H4btca = 1,2,4,5-benzenetetracarboxylic acid; bpe = 1,2-di(4-pyridyl)ethane), constructed using mixed bipyridyl and tetracarboxylate ligands. Single-crystal X-ray diffraction (SC-XRD) indicates that the change of synthetic solvents leads to a significant tuning of structural dimensionality from 2D to 3D framework. Temperature-dependent SC-XRD reveals anisotropically negative and positive thermal expansion of the compounds identified along different crystallographic axes within the frameworks over a 120–400 K temperature range. N2 adsorption measurements indicate a nonporous and ultramicroporous framework for 1 and 2, respectively. Magnetic measurements indicate an easy-plane magnetic anisotropy of the Co2+ ions in the MOFs, with experimental D values of 63.1 and 87.1 cm−1. The ac susceptibility measurements of 1 and 2 show field-induced slow magnetic relaxation below 6 K through different relaxation dynamics. This work not only provides two new cobalt(II) SIM-MOFs, but also presents an effective bipyridyl-tetracarboxylate strategy for designing and building framework materials with interesting magnetic and mechanical properties.

Lattice-commensurate skyrmion texture in a centrosymmetric breathing kagome magnet

Skyrmion lattices (SkL) in centrosymmetric materials typically have a magnetic period on the nanometer-scale, so that the coupling between magnetic superstructures and the underlying crystal lattice cannot be neglected. We reveal the commensurate locking of a SkL to the atomic lattice in Gd3Ru4Al12 via high-resolution resonant elastic x-ray scattering (REXS). Weak easy-plane magnetic anisotropy, demonstrated here by a combination of ferromagnetic resonance and REXS, penalizes placing a skyrmion core on a site of the atomic lattice. Under these conditions, a commensurate SkL, locked to the crystal lattice, is stable at finite temperatures – but gives way to a competing incommensurate ground state upon cooling. We discuss the role of Umklapp-terms in the Hamiltonian for the formation of this lattice-locked state, its magnetic space group, and the role of slight discommensurations, or (line) defects in the magnetic texture. We also contrast our findings with the case of SkLs in noncentrosymmetric material platforms.

New insight into tuning magnetic phases of RMn6Sn6 kagome metals

Predicting magnetic ordering in kagome compounds offers the possibility of harnessing topological or flat-band physical properties through tuning of the magnetism. Here, we examine the magnetic interactions and phases of ErMn6Sn6 which belongs to a family of RMn6Sn6, R = Sc, Y, Gd–Lu, compounds with magnetic kagome Mn layers, triangular R layers, and signatures of topological properties. Using results from single-crystal neutron diffraction and mean-field analysis, we find that ErMn6Sn6 sits close to the critical boundary separating the spiral-magnetic and ferrimagnetic ordered states typical for non-magnetic versus magnetic R layers, respectively. Finding interlayer magnetic interactions and easy-plane Mn magnetic anisotropy consistent with other members of the family, we predict the existence of a number of temperature and field dependent collinear, noncollinear, and noncoplanar magnetic phases. We show that thermal fluctuations of the Er magnetic moment, which act to weaken the Mn-Er interlayer magnetic interaction and quench the Er magnetic anisotropy, dictate magnetic phase stability. Our results provide a starting point and outline a multitude of possibilities for studying the behavior of Dirac fermions in RMn6Sn6 compounds with control of the Mn spin orientation and real-space spin chirality.

Atomic-scale magnetic doping of monolayer stanene by revealing Kondo effect from self-assembled Fe spin entities

Atomic-scale spin entity in a two-dimensional topological insulator lays the foundation to manufacture magnetic topological materials with single atomic thickness. Here, we have successfully fabricated Fe monomer, dimer and trimer doped in the monolayer stanene/Cu(111) through a low-temperature growth and systematically investigated Kondo effect by combining scanning tunneling microscopy/spectroscopy (STM/STS) with density functional theory (DFT) and numerical renormalization group (NRG) method. Given high spatial and energy resolution, tunneling conductance (dI/dU) spectra have resolved zero-bias Kondo resonance and resultant magnetic-field-dependent Zeeman splitting, yielding an effective spin Seff = 3/2 with an easy-plane magnetic anisotropy on the self-assembled Fe atomic dopants. Reduced Kondo temperature along with attenuated Kondo intensity from Fe monomer to trimer have been further identified as a manifestation of Ruderman-Kittel-Kasuya-Yosida (RKKY) interaction between Sn-separated Fe atoms. Such magnetic Fe atom assembly in turn constitutes important cornerstones for tailoring topological band structures and developing magnetic phase transition in the single-atom-layer stanene.

МАГНИТНЫЕ И СТРУКТУРНЫЕ СВОЙСТВА СПЛАВОВ ГЕЙСЛЕРА MN-NI-TI, ПОЛНОСТЬЮ СОСТОЯЩИХ ИЗ ПЕРЕХОДНЫХ МЕТАЛЛОВ

The paper presents a theoretical study of the effect of different atomic and magnetic orderings on the structural and magnetic properties of Mn2Ni1+xTi1-x alloys, which are composed entirely of transition metals. Using the density functional theory, we predict the structural ground states and magnetic reference states of compounds with x = 0, 0,25, 0,5, and 0,75 in both cubic austenite and tetragonal martensite phases. Partial substitution of Ti atoms with Ni leads to an increase in the energy barrier between structural phases, to a change from a layered atomic ordering to an alternating staggered order, and to a change from antiferromagnetic to ferromagnetic spin alignment in the cubic phase. All compounds with tetragonally distorted structures reveal the out-ofplane spin configuration and easy axis magnetocrystalline anisotropy except tetragonal L10 phase of Mn2NiTi. For the latter structure, easy-plane magnetic anisotropy is observed. The calculated values of anisotropy are comparable with those of tetragonal L10-FeNi.

Control of the geometry and anisotropy driven by the combination of steric and anion coordination effects in CoII complexes with N6-tripodal ligands: the impact of the size of the ligand on the magnetization relaxation time.

Four mononuclear CoII complexes of formula [Co(L)(SCN)2(CH3OH)0.5(H2O)0.5]·1.5H2O·0.75CH3OH (1), [Co(L1)Cl2]·H2O·2CH3CN (2), [Co(L1)(SCN)2]·1.5H2O·CH3OH (3) and [Co(L1)]ClO4·2CH3OH (4) were prepared from the N6-tripodal Schiff base ligands (S)P[N(Me)NC(H)2-Q]3 (L) and (S)P[N(Me)NC(H)1-ISOQ]3 (L1), where Q and ISOQ represent quinolyl and isoquinolyl moieties, respectively. In 1, the L ligand does not coordinate to the CoII ion in a tripodal manner but using a new N,N,S tridentate mode, which is due to the fact that the N6-tripodal coordination promotes a strong steric hindrance between the quinolyl moieties. However, L1 can coordinate to the CoII ions either in a tripodal manner using CoII salts with poorly coordinating anions to give 4 or in a bisbidentate fashion using CoII salt-containing medium to strongly coordinating anions to afford 2 and 3. In the case of L1, there is no steric hindrance between ISOQ moieties after coordination to the CoII ion. The CoII ion exhibits a distorted octahedral geometry for compounds 1-3, with the anions in cis positions for the former and in trans positions for the two latter compounds. Compound 4 shows an intermediate geometry between an octahedral and trigonal prism but closer to the latter one. DC magnetic properties, HFEPR and FIRMS measurements and ab initio calculations demonstrate that distorted octahedral complexes 1-3 exhibit easy-plane magnetic anisotropy (D > 0), whereas compound 4 shows large easy-axis magnetic anisotropy (D < 0). Comparative analysis of the magneto-structural data underlines the important role that is played not only by the coordination geometry but also the electronic effects in determining the anisotropy of the CoII ions. Compounds 2-3 show a field-induced slow relaxation of magnetization. Despite its large easy-axis magnetic anisotropy, compound 4 does not show significant slow relaxation (SMR) above 2 K under zero applied magnetic fields, but its magnetic dilution with ZnII triggers SMR at zero field. Finally, it is worth remarking that compounds 2-4 show smaller relaxation times than the analogous complexes with the tripodal ligand bearing in its arms pyridine instead of isoquinoline moieties, which is most likely due to the increase of the molecular size in the former one.

Nonlinear dynamics of magnetic multilayers and low-dimensional magnets. i. easy-plane magnetic anisotropy

The nonlinear dynamics of two magnetic elements with easy-plane magnetic anisotropy and ferromagnetic exchange interaction is considered in the framework of discrete Landau–Lifshitz equations. In the absence of damping, exact solutions of these equations are obtained for the proposed integrable dynamical system. The dynamics of the system, its frequency characteristics, and essentially nonlinear high-amplitude excitations, in particular, with a non-equal distribution of excitation between magnetic elements, have been fully investigated. The results of a theoretical study can be used in the analysis of dynamics of magnetic multilayers excited by a polarized current or a high-frequency field.

Desolvation-induced magnetic switching from single-ion magnetism to spin-crossover in a halogen-functionalized cobalt(II) complex

The switching between spin-crossover (SCO) and single-ion magnet (SIM) are fascinating because the process provides potential in-depth understating of different bistability. Herein, we present a rare example of the desolvation-induced magnetic switching from single-ion magnetism to SCO between a halogen-functionalized cobalt(II) complex, [Co(Brphtpy)2](PF6)2·2MeOH (Brphtpy = 4′-(4-Bromophenyl)-2,2′:6′,2′'-terpyridine, 1·2MeOH) and its desolvated material of [Co(Brphtpy)2](PF6)2 (1). The temperature-dependent magnetic susceptibility and variable-temperature single crystal X-ray diffraction results show a high spin state of the Co(II) ions in 1·2MeOH. At lower temperature, frequency- and temperature-dependent slow magnetic relaxation behaviors were evidenced under an applied dc field of 1000Oe, originating from the easy-plane magnetic anisotropy (D=43.5 cm−1) of Co(II) ions. After the release of methanol molecules, interestingly, the desovated material 1 display a complete and cooperative two-step spin transitions with transition temperatures being 350 and 125K. Differential scanning calorimetry measurements support the stepwise SCO behavior and reveal the related ΔH and ΔS.

Easy-plane spin Hall oscillator

Spin Hall oscillators (SHOs) based on bilayers of a ferromagnet (FM) and a non-magnetic heavy metal (HM) are electrically tunable nanoscale microwave signal generators. Achieving high output power in SHOs requires driving large-amplitude magnetization dynamics by a direct spin Hall current. Here we present an SHO engineered to have easy-plane magnetic anisotropy oriented normal to the bilayer plane, enabling large-amplitude easy-plane dynamics driven by spin Hall current. Our experiments and micromagnetic simulations demonstrate that the easy-plane anisotropy can be achieved by tuning the magnetic shape anisotropy and perpendicular magnetic anisotropy in a nanowire SHO, leading to a significant enhancement of the generated microwave power. The easy-plane SHO experimentally demonstrated here is an ideal candidate for realization of a spintronic spiking neuron. Our results provide an approach to design of high-power SHOs for wireless communications, neuromorphic computing, and microwave assisted magnetic recording.

Low-temperature antiferromagnetic order in orthorhombic CePdAl3

We report the magnetization, ac susceptibility, and specific heat of optically float-zoned single crystals of ${\mathrm{CePdAl}}_{3}$. In comparison to the properties of polycrystalline ${\mathrm{CePdAl}}_{3}$ reported in the literature, which displays a tetragonal crystal structure and no long-range magnetic order, our single crystals exhibit an orthorhombic structure ($Cmcm$) and antiferromagnetic order below a N\'eel temperature ${T}_{1}=5.6$ K. The specific heat at zero field shows two anomalies, namely, a broad transition at ${T}_{1}=5.6$ K followed by a $\ensuremath{\lambda}$-anomaly at ${T}_{2}=5.4$ K. A conservative estimate of the Sommerfeld coefficient of the electronic specific heat, $\ensuremath{\gamma}=121\phantom{\rule{0.28em}{0ex}}\mathrm{mJ}\phantom{\rule{0.16em}{0ex}}{\mathrm{K}}^{\ensuremath{-}2}\phantom{\rule{0.16em}{0ex}}{\mathrm{mol}}^{\ensuremath{-}1}$, indicates a moderately enhanced heavy-fermion ground state. A twin microstructure evolves in the family of planes spanned by the basal plane lattice vectors ${\mathbf{a}}_{\mathrm{o}}$ and ${\mathbf{c}}_{\mathrm{o}}$ , with the magnetic hard axis ${\mathbf{b}}_{\mathrm{o}}$ common to all twins. The antiferromagnetic state is characterized by a strong a${}_{\mathrm{o}}$, c${}_{\mathrm{o}}$ easy-plane magnetic anisotropy where the a${}_{\mathrm{o}}$ direction is the easy axis in the easy plane. A spin-flop transition induced under magnetic field along the easy directions, results in complex magnetic phase diagrams. Taken together, our results reveal a high sensitivity of the magnetic and electronic properties of ${\mathrm{CePdAl}}_{3}$ to its structural modifications.

Probing the Influence of Structural Distortion and Axial Ligands on Magnetic Anisotropy in a Series of Chiral Pentagonal Bipyramidal Co(II) and Ni(II) Complexes

A series of magnetically anisotropic chiral pentagonal bipyramidal (PBP) Co(II) and Ni(II) complexes are prepared by employing chiral bis-hydrazone ligands, viz., 2,6-diacetylpyridinebis(R/S-lactic acid hydrazide) (R,R/S,S-daplh) and (R)/(S)-2, 6-diacetylpyridinebis(3-hydroxyisobutyric acid hydrazide) (R,R/S,S-daphibh). Investigations of magnetic anisotropy by wave function based ab initio CASSCF calculations manifest the presence of substantial negative uniaxial magnetic anisotropy in the present PBP Ni(II) complexes, while the chiral PBP Co(II) complexes display large easy-plane magnetic anisotropy. Magnetostructural correlations show the profound influence of structural distortions and the ligand field environment on the axial zero field splitting parameter (D). Accordingly, a convenient strategy to enhance the D parameter in PBP Co(II) and Ni(II) complexes is devised.

A Chain of Vertex-Sharing {CoIII2CoII2}n Squares with Single-Ion Magnet Behavior

A new mixed-valence one-dimensional coordination polymer of formula {[CoII(MeOH)2][(μ-NC)2CoIII(dmphen)(CN)2]2}n·2nH2O (1) was obtained by reacting the Ph4P[CoII(dmphen)(CN)3] metalloligand (dmphen = 2,9-dimethyl-1,10-phenanthroline and Ph4P+ = tetraphenylphosphonium ion) with cobalt(II) acetate tetrahydrate. The structural analysis shows the formation of a neutral 4,2-ribbon-like chain of vertex-sharing cyanido-bridged {CoIII2CoII2} squares in which the metalloligand underwent an oxidation process and a reorganization to form {CoIII(dmphen)(CN)4}− linkers that coordinate to the [CoII(MeOH)2]2+ units through single cyanido ligands. Both cobalt(II) and Co(III) cations are six-coordinated in distorted octahedral environments. The shortest intrachain distance between the paramagnetic cobalt(II) ions is 7.36 Å, a value which is shorter than the shortest interchain one (10.36 Å). Variable-temperature (1.9–300 K) static (dc) magnetic measurements for 1 indicate the occurrence of magnetically isolated high-spin cobalt(II) ions with a D value of +67.0 cm−1. Dynamic alternating current (ac) magnetic measurements between 2.0–13 K reveal that 1 exhibits slow magnetic relaxation under non-zero applied dc fields, being thus a new example of field-induced SIM with easy-plane magnetic anisotropy. Theoretical calculations by CASSCF/NEVPT2 on 1 support the results from magnetometry. The relaxation of the magnetization occurs in the ground state under external dc fields through a two-phonon Raman process and one intra-Kramers mechanism.

Influence of crystalline electric field on the magnetic properties of CeCd3X3(X=P,As)

CeCd$_3$P$_3$ and CeCd$_3$As$_3$ compounds adopt the hexagonal ScAl$_3$C$_3$-type structure, where magnetic Ce ions on a triangular lattice order antiferromagnetically below $T_\text{N} \sim$0.42~K. Their crystalline electric field (CEF) level scheme has been determined by fitting magnetic susceptibility curves, magnetization isotherms, and Schottky anomalies in specific heat. The calculated results, incorporating the CEF excitation, Zeeman splitting, and molecular field, are in good agreement with the experimental data. The CEF model, with Ce$^{3+}$ ions in a trigonal symmetry, explains the strong easy-plane magnetic anisotropy that has been observed in this family of materials. A detailed examination of the CEF parameters suggests that the fourth order CEF parameter $B_{4}^{3}$ is responsible for the strong CEF induced magnetocrystalline anisotropy, with a large $ab$-plane moment and a small $c$-axis moment. The reliability of our CEF analysis is assessed by comparing the current study with earlier reports of CeCd$_{3}$As$_{3}$. For both CeCd$_{3}X_{3}$ ($X$ = P and As) compounds, less than 40 \% of $R\ln(2)$ magnetic entropy is recovered by $T_\text{N}$ and full $R\ln(2)$ entropy is achieved at the Weiss temperature $\theta_{p}$. Although the observed magnetic entropy is reminiscent of delocalized 4$f$-electron magnetism with significant Kondo screening, the electrical resistivity of these compounds follows a typical metallic behavior. Measurements of thermoelectric power further validate the absence of Kondo contribution in CeCd$_{3}X_{3}$.

Spontaneous Biskyrmion Lattice in a Centrosymmetric Rhombohedral Rare-Earth Magnet with Easy-Plane Anisotropy.

Magnetic skyrmion and its derivatives have demonstrated fascinating topological behaviors with potential applications in future spintronic devices. Despite the recent progress, the spontaneous skyrmion lattice and successive topological transition in the magnets with easy-plane magnetic anisotropy are still elusive especially at room temperature. Here, in a centrosymmetric rhombohedral Nd2Co17 magnet with easy-plane magnetic anisotropy, spontaneous biskyrmions are observed over a wide temperature range across room temperature, and then evolve into enclosed in-plane domains with nanometric size due to the enhancement of the planar magnetic anisotropy. The spontaneous generation of the biskyrmion lattice and its evolution along different crystal orientations demonstrate the crucial role of intrinsic bi-anisotropy and demagnetization effects. This discovery provides a fundamental insight into the nature of topological magnetic textures in easy-plane anisotropy materials and suggests an arena to explore the topological states in rare-earth magnets as well as their applications in spintronics.

Field-induced single-ion magnet behavior in a cobalt(II) coordination polymer constructed by a mixed bipyridyl-tetracarboxylate strategy

A porous two-dimensional (2D) cobalt(II) metal–organic framework (MOF), {[Co(H2tbca)(bpb)(H2O)2]·bpb}n (H4tbca = 1,2,4,5-Benzenetetracarboxylic acid; bpb = 1,4-bis(pyrid-4-yl)benzene), was synthesized and structurally characterized. Single crystal X-ray diffraction analysis indicates that the monometallic Co2+ ion acted as coordination nodes in a distorted octahedral geometry and bridged by H2tbca2− and bpb ligands, giving rise to a porous 2D sql network. Thermal analysis reveals high thermal stability of the framework material even losing its guest molecules. Magnetic studies showed that the six-coordinated Co2+ ions exhibit large easy-plane magnetic anisotropy with the zero-field splitting parameter D = 62.1 cm−1. For the presence of significant single-ion magnetic anisotropy, single-ion magnet (SIM) behavior through combined Direct and Raman mechanisms was evidenced with the effective energy Ueff = 31.8 cm−1. The forgoing result provides a new 2D cobalt(II) SIM-MOF and a potential bipyridyl-tetracarboxylate approach for the construction of SIM frameworks.

Fine‐Tuning of Structural Distortion and Magnetic Anisotropy by Organosulfonates in Octahedral Cobalt(II) Complexes

Comprehensive SummaryPrecise modulation of the magnetic anisotropy of metal ions remains highly important for the development of high–performance single‐molecule magnets (SMMs). We herein reported the synthetic, structural, spectral, magnetic, and computational studies on four mononuclear CoII complexes in a distorted octahedral environment. The change of the organosulfonate anions triggers significant modification of the distorted octahedral CoN6 coordination sphere, which enables us to tackle the influence of the structural distortion on the magnetic anisotropy in these complexes. Magnetic measurements revealed that the four complexes possess easy–plane magnetic anisotropy with large and positive zero‐field splitting parameters, which decrease with the increasing distortion of the pseudo–octahedral CoII coordination geometry. This correlation was further confirmed by high–frequency/–field EPR (HF–EPR) spectra and theoretical calculations. Dynamic magnetic susceptibility measurements indicate that these complexes both exhibit slow magnetic relaxation under an external dc field, indicating the field‐induced single‐ion magnets (SIMs) of the four complexes. These results indicate that structural distortion plays an important role in the magnetic anisotropy of CoII complexes and should be carefully considered in the design of molecular complexes with high magnetic anisotropy.

Slow Magnetic Relaxation of Dy Adatoms with In-Plane Magnetic Anisotropy on a Two-Dimensional Electron Gas.

We report on the magnetic properties of Dy atoms adsorbed on the (001) surface of SrTiO3. X-ray magnetic circular dichroism reveals slow relaxation of the Dy magnetization on a time scale of about 800 s at 2.5 K, unusually associated with an easy-plane magnetic anisotropy. We attribute these properties to Dy atoms occupying hollow adsorption sites on the TiO2-terminated surface. Conversely, Ho atoms adsorbed on the same surface show paramagnetic behavior down to 2.5 K. With the help of atomic multiplet simulations and first-principles calculations, we establish that Dy populates also the top-O and bridge sites on the coexisting SrO-terminated surface. A simple magnetization relaxation model predicts these two sites to have an even longer magnetization lifetime than the hollow site. Moreover, the adsorption of Dy on the insulating SrTiO3 crystal leads, regardless of the surface termination, to the formation of a spin-polarized two-dimensional electron gas of Ti 3dxy character, together with an antiferromagnetic Dy–Ti coupling. Our findings support the feasibility of tuning the magnetic properties of the rare-earth atoms by acting on the substrate electronic gas with electric fields.

Hydrogen-Bonded Framework of a Cobalt(II) Complex Showing Superior Stability and Field-Induced Slow Magnetic Relaxation.

A unique hydrogen-bonded organic-inorganic framework (HOIF) constructed from a mononuclear cobalt(II) complex, [Co(MCA)2·(H2O)2] (HMCA = 4-imidazolecarboxylic acid), via multiple hydrogen-bonding interactions was synthesized and structurally characterized. The Co(II) center in the HOIF features a highly distorted octahedral coordination environment. Remarkably, the CoII HOIF showed permanent porosity with superior stability as established by combined thermogravimetric analysis (TGA), variable-temperature infrared spectra (IR), variable-temperature powder X-ray diffraction data (PXRD), and a CO2 isotherm. Structural studies reveal that short multiple hydrogen bonds should be responsible for the superior thermal and chemical stability of a HIOF. Magnetic investigations reveal the large easy-plane magnetic anisotropy of the Co2+ ions with the fitted D values being 22.1 (magnetic susceptibility and magnetization data) and 29.1 cm-1 (reduced magnetization data). In addition, the HOIF exhibits field-induced slow magnetic relaxation at low temperature with an effective energy barrier of Ueff = 45.2 cm-1, indicative of a hydrogen-bonded framework single-ion magnet of the compound. The origin of the significant magnetic anisotropy of the complex was also understood from computational studies. In addition, BS-DFT calculations indicate that the superexchange interactions between the neighboring CoII ions are non-negligible antiferromagnetism with JCo-Co = -0.5 cm-1. The foregoing results provide not only a carboxylate-imidazole ligand approach toward a stable HOIF but also a promising way to build a robust single-ion magnet via hydrogen-bond interactions.

Modulation of the magnetic dynamics of pentagonal-bipyramidal Co(II) complexes by fine-tuning the coordination microenvironment.

Four air-stable mononuclear Co(II) complexes, with the formulas [Co(dapbh)(H2O)(CH3OH)] (1), [Co(Hdapbh)(N3)(CH3OH)]·(CH3OH) (2), [Co(H2aapbh)(CH3OH)2]·(NO3)2 (3) and [Co(H2bapbh)(H2O)(NO3)]·(NO3) (4), have been synthesized and structurally characterized by single crystal X-ray diffraction. In all of the complexes, the Co(II) centers constrained by the rigid pentadentate ligand H2LR with two protonable hydrogens adopt a heptacoordinated pentagonal-bipyramidal geometry. The combined analyses of magnetic data and ab initio calculations unveil large easy-plane magnetic anisotropies for these complexes (D = +37.338, +37.273, +41.138 and +41.139 cm-1 for 1-4, respectively), which indicate that the chemical alterations of the equatorial ligand and the ligand field strength in the axial positions synergistically fine-tune the magnitude of the D values. Magnetic investigations demonstrate the field-induced single-ion magnetic behavior in complexes 1, 2 and 4 with diverse energy barriers (Ueff) of 12.25 for 1, 44.15 for 2 and 48.72 K for 4, corresponding to the geometrical distortion of the heptacoordinated Co(II) ion. That is, the greatest deviation from the ideal D5h symmetry in 4 is responsible for the highest barrier.

Field-induced single-ion magnet behavior in a hydrogen-bonded supramolecular cobalt(II) complex

Hydrogen-bonded supramolecular frameworks remain highly interesting for the development of novel porous materials. Herein a hydrogen-bonded supramolecular framework of a cobalt(II) complex, [Co(cpt)2(H2O)2] (Hcpt = 4-(p-carboxyphenyl)-1,2,4-triazole), was synthesized and structurally characterized. A single crystal X-ray diffraction (SC-XRD) study indicates that the monometallic Co2+ ion is located in a distorted octahedral geometry and the complex forms a two-dimensional supramolecular network stabilised by significant intermolecular N···H interactions. Variable-temperature PXRD and TGA analysis experiments revealed considerable thermal stability of the supramolecular framework of the CoII complex. Magnetic studies showed that the distorted octahedral Co2+ ion exhibits considerable easy-plane magnetic anisotropy with D = 22.3 cm−1, while field-induced single-ion magnet (SIM) behavior was evidenced at low temperature. The forgoing results further highlight that the hydrogen-bonded supramolecular framework could be used as a great platform for the development of molecular nanomagnets.