Magnetization Of Single Crystals Research Articles

Magnetic structure, excitations, and field-induced transitions in the honeycomb lattice compound Er2Si2O7

We investigate the magnetic properties of the monoclinic D-type Er2Si2O7 with a distorted honeycomb lattice using powder and single-crystal neutron scattering techniques, as well as single-crystal magnetization measurements. The powder neutron diffraction shows that below the ordering temperature, TN=1.85K, the compound forms a q=0 antiferromagnetic structure with four sublattices. For H∥a, magnetization measurements reveal a narrow but clearly visible plateau at one-third of the magnetization saturation value. The plateau's stabilization is accompanied by a significant increase of the magnetic unit cell, as the magnetic peaks with fractional indices are observed in single-crystal neutron diffraction experiments. At low temperatures, the inelastic neutron scattering measurements reveal the presence of low-energy, almost dispersionless excitations. Their spectrum is sensitive to the applied field, it significantly softens on the magnetization plateau, and demonstrates the behavior expected for a noncollinear Ising antiferromagnet away from the plateau. Published by the American Physical Society 2024

Field-induced magnetic states in geometrically frustrated SrEr2O4

We report an unusual in-field behaviour of SrEr_22O_44 for a magnetic field applied along two high-symmetry directions, the a and c axes. This geometrically frustrated magnet hosts two crystallographically inequivalent Er ions, Er1 and Er2, that are both located on triangular zigzag ladders, but only one site, Er1, forms a long-range magnetic order at low temperatures in a zero field. We follow the sequence of peculiar field induced states in SrEr_22O_44 with detailed single-crystal magnetisation and neutron diffraction experiments. On application of an external field along the cc axis, the long-range antiferromagnetic order of the Er1 ions is rapidly destroyed and replaced, in fields between 2 and 5 kOe, by a state with shorter-range correlations. The change in correlation length coincides with a fast increase in magnetisation during the metamagnetic transition above which a long-range order is reestablished and maintained into the high fields. The high-field ferromagnet-like order is characterised by significantly different magnetic moments on the two Er sites, with the Er1 site dominating the magnetisation process. For the field applied parallel to the a axis, in the field range of 4 to 12 kOe, the planes of diffuse magnetic scattering observed in zero field due to the one-dimensional correlations between the Er2 moments are replaced by much more localised but still diffuse features corresponding to the establishment of an up-up-down structure associated with a one-third magnetisation plateau. Above 14 kOe, a ferromagnet-like high-field order is induced following another phase transition. For this direction of the field, the Er2 moments dictate the succession of transitions while the Er1 moments remain significantly less polarised. A complete field polarisation of both Er sites is not achieved even at 50~kOe for either field direction, reflecting the strongly anisotropic nature of magnetisation process in SrEr_22O_44.

Mode Crystallography Analysis through the Structural Phase Transition and Magnetic Critical Behavior of the Lacunar Spinel GaMo4Se8.

In the lacunar spinels, with the formula AB4X8, transition-metal ions form tightly bound B4 clusters resulting in exotic physical properties such as the stabilization of Néel-type skyrmion lattices, which hold great promise for energy-efficient switching devices. These properties are governed by the symmetry of these compounds with distortion of the parent noncentrosymmetric F4̅3m space group to the polar R3m, with recent observation of a coexisting Imm2 low-temperature phase. In this study, through powder neutron diffraction, we further confirm that a metastable Imm2 coexists with the R3m phase in GaMo4Se8 and we present its structure. By applying the mode crystallography approach to the distortions together with anisotropic microstrain broadening analysis, we postulate that the formation origin of the minority Imm2 phase stems from the high compressive stress observed in the R3m phase. Bond valence sum analysis also suggests a change in electronic configuration in the transition to Imm2 which could have implications on the electrical properties of the compound. We further establish the nature of the magnetic phase transition using critical exponent analysis obtained from single-crystal magnetization measurements which shows a mixture of tricritical mean-field and 3D Heisenberg behavior [β = 0.22(4), γ = 1.19(1), and δ = 6.42(1)]. Magnetoentropic mapping performed on a single crystal reveals the signature of a positive entropy region near the magnetic phase transition which corresponds to the skyrmion phase field observed in a polycrystalline sample.

Orbital crossing in spin-split Fermi surfaces and anisotropic effective mass of the noncentrosymmetric heavy-fermion paramagnet UPt5

We report the single-crystal growth of the noncentrosymmetric cubic heavy-fermion paramagnet ${\mathrm{UPt}}_{5}$ and comparative Fermi surface studies of de Haas-van Alphen (dHvA) experiments and theoretical band calculations. We also present the results of single-crystal x-ray diffraction, electrical resistivity, heat capacity, and magnetization measurements using single crystals of ${\mathrm{UPt}}_{5}$. The dHvA experiments reveal nearly spherical split hole Fermi surfaces and largely split electron Fermi surfaces, which are in agreement with the results of a band-structure calculation. The largely split electron Fermi surfaces may be understood through the antisymmetric spin-orbit interaction derived from U-$5f$ and Pt-$5d$ electrons. We explain the observed unexpected dHvA frequencies quasiquantitatively based on orbital crossing using the coupled network analysis in the split hole Fermi surface pair. Furthermore, the temperature dependence of the dHvA amplitude reveals enhanced cyclotron effective masses of up to $29{m}_{0}$ and a peculiar anisotropic effective mass in the paramagnetic cubic heavy-fermion ${\mathrm{UPt}}_{5}$.

Magnetic Properties and Electronic Structure of the S = 2 Complex [MnIII{(OPPh2)2N}3] Showing Field-Induced Slow Magnetization Relaxation

The high-spin S = 2 Mn(III) complex [Mn{(OPPh2)2N}3] (1Mn) exhibits field-induced slow relaxation of magnetization (Inorg. Chem. 2013, 52, 12869). Magnetic susceptibility and dual-mode X-band electron paramagnetic resonance (EPR) studies revealed a negative value of the zero-field-splitting (zfs) parameter D. In order to explore the magnetic and electronic properties of 1Mn in detail, a combination of experimental and computational studies is presented herein. Alternating-current magnetometry on magnetically diluted samples (1Mn/1Ga) of 1Mn in the diamagnetic gallium analogue, [Ga{(OPPh2)2N}3], indicates that the slow relaxation behavior of 1Mn is due to the intrinsic properties of the individual molecules of 1Mn. Investigation of the single-crystal magnetization of both 1Mn and 1Mn/1Ga by a micro-SQUID device reveals hysteresis loops below 1 K. Closed hysteresis loops at a zero direct-current magnetic field are observed and attributed to fast quantum tunneling of magnetization. High-frequency and -field EPR (HFEPR) spectroscopic studies reveal that, apart from the second-order zfs terms (D and E), fourth-order terms (B4m) are required in order to appropriately describe the magnetic properties of 1Mn. These studies provide accurate spin-Hamiltonian (sH) parameters of 1Mn, i.e., zfs parameters |D| = 3.917(5) cm-1, |E| = 0.018(4) cm-1, B04 = B42 = 0, and B44 = (3.6 ± 1.7) × 10-3 cm-1 and g = [1.994(5), 1.996(4), 1.985(4)], and confirm the negative sign of D. Parallel-mode X-band EPR studies on 1Mn/1Ga and CH2Cl2 solutions of 1Mn probe the electronic-nuclear hyperfine interactions in the solid state and solution. The electronic structure of 1Mn is investigated by quantum-chemical calculations by employing recently developed computational protocols that are grounded on ab initio wave function theory. From computational analysis, the contributions of spin-spin and spin-orbit coupling to the magnitude of D are obtained. The calculations provide also computed values of the fourth-order zfs terms B4m, as well as those of the g and hyperfine interaction tensor components. In all cases, a very good agreement between the computed and experimentally determined sH parameters is observed. The magnetization relaxation properties of 1Mn are rationalized on the basis of the composition of the ground-state wave functions in the absence or presence of an external magnetic field.

Nonmetallic Inclusions in Alloys of the Fe – Co – Ni – Cu – Al – Ti System with Hafnium and Niobium

Nonmetallic inclusions in magnetic alloys of the Fe – Co – Ni – Cu – Al – Ti system with additions of niobium and hafnium used in the production of single-crystal permanent magnets are studied. The kinds of inclusions in magnetic alloys are determined with the help of rapid analysis of the chemical composition, optical and electron microscopy, quantitative microscopic x-ray spectrum analysis, and electron back-scatter diffraction. The phase compositions are computed with the help of the Thermo-Calc software.

Experimental determination of single molecule toroic behaviour in a Dy8 single molecule magnet.

The enhancement of toroic motifs through coupling toroidal moments within molecular nanomagnets is a new, interesting and relevant approach for both fundamental research and potential quantum computation applications. We investigate a Dy8 molecular cluster and discover it has a antiferrotoroic ground state with slow magnetic relaxation. The experimental characterization of the magnetic anisotropy axes of each magnetic center and their exchange interactions represents a considerable challenge due to the non-magnetic nature of the toroidal motif. To overcome this and obtain access to the low energy states of Dy8 we establish a multi-orientation single-crystal micro Hall sensor magnetometry approach. Using an effective Hamiltonian model we then unpick the microscopic spin structure of Dy8, leading to a canted antiferrotoroidic tetramer molecular ground state. These findings are supported with electrostatic calculations that independently confirm the experimentally determined magnetic anisotropy axes for each DyIII ion within the molecule.

Study of the Effect of Hafnium on the Magnetic Properties of Permanent Magnets with Single-Crystal Structure from Alloy YuNDKT5AA

The causes of the action of hafnium additives on the magnetic properties of single-crystal permanent magnets from alloy YuNDKT5AA are studied. The temperature regimes of the isothermal magnetic treatment of single-crystal permanent magnets from alloy YuNDKT5AA with a hafnium additive is corrected. Anew mode of multistage tempering is suggested and an operation of thermal stabilization of permanent magnets is introduced.

Single-Ion Anisotropy Estimates for the Rhenium(IV-Based) Molecular Magnets: Modeling and Simulations Studies

We prove that the tetranuclear oxalato-bridged complex Re3(IV)Ni(II) demonstrating the single molecule magnet behavior is a good anisotropic spin Heisenberg model. Our comprehensive analysis, based on an exact diagonalisation technique, genetic algorithm ideas, and EPR resonances, leads to a unique set of the single-ion anisotropy parameters (DRe/kB = −8.8 K, DNi/kB = 9.9 K, E = 0). The parameters determine the model that quantitatively describes the zero-field splitting as well as the temperature dependence of magnetic susceptibility and the field dependence of single-crystal magnetisation isotherms, they also reveal pronounced maxima in the field dependence of the differences between the transverse magnetisation components, which are directly related to the rhombicity factor E/D. They are noticeable enough to be detected experimentally and also occur for mononuclear complexes. Finally, we propose the rationale for the unusual reduction in the energy barrier with respect to the zero-field splitting.

Characterization of the spin-12linear-chain ferromagnet CuAs2O4

The magnetic and lattice properties of the $S=1/2$ quantum-spin-chain ferromagnet CuAs${}_{2}$O${}_{4}$, mineral name trippkeite, were investigated. The crystal structure of CuAs${}_{2}$O${}_{4}$ is characterized by the presence of corrugated CuO${}_{2}$ ribbon chains. Measurements of the magnetic susceptibility, heat capacity, electron paramagnetic resonance, and Raman spectroscopy were performed. Our experiments conclusively show that a ferromagnetic transition occurs at $\ensuremath{\sim}$7.4 K. Ab initio DFT calculations reveal dominant ferromagnetic nearest-neighbor and weaker antiferromagnetic next-nearest-neighbor spin exchange interactions along the ribbon chains. The ratio of ${J}_{\mathrm{nn}}$/${J}_{\mathrm{nnn}}$ is near $\ensuremath{-}$4, placing CuAs${}_{2}$O${}_{4}$ in close proximity to a quantum critical point in the ${J}_{\mathrm{nn}}$-${J}_{\mathrm{nnn}}$ phase diagram. TMRG simulations used to analyze the magnetic susceptibility confirm this ratio. Single-crystal magnetization measurements indicate that a magnetic anisotropy forces the Cu${}^{2+}$ spins to lie in an easy plane perpendicular to the $c$ axis. An analysis of the field- and temperature-dependent magnetization by modified Arrott plots reveals a 3d-$X$Y critical behavior. Lattice perturbations induced by quasihydrostatic pressure and temperature were mapped via magnetization and Raman spectroscopy.

Slow Magnetization Relaxation in a 1-D Double-Chain Coordination Polymer Composed of {Dy<sup>III</sup> <sub>4</sub>} Repeating Units

The “unsuccessful” synthesis of the non-commercially available ‘Dy(O2CPh)3’ precursor from the stoichiometric reaction of Dy(NO3)3·5H2O with 3 equivalents of NaO2CPh in MeCN/H2O has led instead to the “successful” isolation and structural characterization of the 1-D coordination polymer [Dy4(O2CPh)12(H2O)8]n·2n(PhCO2H)·n(MeCN) (1·2n(PhCO2H)·n(MeCN)) in excellent yields (~90%). The one-dimensional double-chain structure of 1 was resulted from the linkage of two parallel chains by syn,anti-η1:η1:µ PhCO2 - groups. The lattice structure of 1 is further extended to a 2-D network through hydrogen bonding and Π-Π stacking interactions. The observation of out-of-phase (χ"M) ac susceptibility signals suggested that 1 might be a molecular nanomagnet, and this was confirmed by single-crystal magnetization vs. dc field sweeps that exhibited hysteresis, the diagnostic property of a magnet.

A New Family of Trinuclear Nickel(II) Complexes as Single‐Molecule Magnets

Three new trinuclear nickel (II) complexes with the general composition [Ni3 L3 (OH)(X)](ClO4 ) have been prepared in which X=Cl(-) (1), OCN(-) (2), or N3(-) (3) and HL is the tridentate N,N,O donor Schiff base ligand 2-[(3-dimethylaminopropylimino)methyl]phenol. Single-crystal structural analyses revealed that all three complexes have a similar Ni3 core motif with three different types of bridging, namely phenoxido (μ2 and μ3 ), hydroxido (μ3 ), and μ2 -Cl (1), μ1,1 -NCO (2), or μ1,1 -N3 (3). The nickel(II) ions adopt a compressed octahedron geometry. Single-crystal magnetization measurements on complex 1 revealed that the pseudo-three-fold axis of Ni3 corresponds to a magnetic easy axis, being consistent with the magnetic anisotropy expected from the coordination structure of each nickel ion. Temperature-dependent magnetic measurements indicated ferromagnetic coupling leading to an S=3 ground state with 2J/k=17, 17, and 28 K for 1, 2, and 3, respectively, with the nickel atoms in an approximate equilateral triangle. The high-frequency EPR spectra in combination with spin Hamiltonian simulations that include zero-field splitting parameters DNi /k=-5, -4, and -4 K for 1, 2, and 3, respectively, reproduced the EPR spectra well after a anisotropic exchange term was introduced. Anisotropic exchange was identified as Di,j /k=-0.9, -0.8, and -0.8 K for 1, 2, and 3, respectively, whereas no evidence of single-ion rhombic anisotropy was observed spectroscopically. Slow relaxation of the magnetization at low temperatures is evident from the frequency-dependence of the out-of-phase ac susceptibilities. Pulsed-field magnetization recorded at 0.5 K shows clear steps in the hysteresis loop at 0.5-1 T, which has been assigned to quantum tunneling, and is characteristic of single-molecule magnets.

Comproportionation Reactions to Manganese(III/IV) Pivalate Clusters: A New Half-Integer Spin Single-Molecule Magnet

The comproportionation reaction between Mn(II) and Mn(VII) reagents under acidic conditions has been investigated in the presence of pivalic acid as a route to new high oxidation state manganese pivalate clusters containing some Mn(IV). The reaction of Mn(O(2)CBu(t))(2) and NBu(n)(4)MnO(4) with an excess of pivalic acid in the presence of Mn(ClO(4))(2) and NBu(n)(4)Cl in hot MeCN led to the isolation of [Mn(8)O(6)(OH)(O(2)CBu(t))(9)Cl(3)(Bu(t)CO(2)H)(0.5)(MeCN)(0.5)] (1). In contrast, the reaction of Mn(NO(3))(2) and NBu(n)(4)MnO(4) in hot MeCN with an excess of pivalic acid gave a different octanuclear complex, [Mn(8)O(9)(O(2)CBu(t))(12)] (2). The latter reaction but with Mn(O(2)CBu(t))(2) in place of Mn(NO(3))(2), and in a MeCN/THF solvent medium, gave [Mn(9)O(7)(O(2)CBu(t))(13)(THF)(2)] (3). Complexes 1-3 possess rare or unprecedented Mn(x) topologies: 1 possesses a [Mn(III)(7)Mn(IV)(μ(3)-O)(4)(μ(4)-O)(2)(μ(3)-OH)(μ(4)-Cl)(μ(2)-Cl)](8+) core consisting of two body-fused Mn(4) butterfly units attached to the remaining Mn atoms via bridging O(2-), OH(-), and Cl(-) ions. In contrast, 2 possesses a [Mn(6)(IV)Mn(2)(III)(μ(3)-O)(6)(μ-O)(3)](12+) core consisting of two [Mn(3)O(4)] incomplete cubanes linked by their O(2-) ions to two Mn(III) atoms. The cores of 1 and 2 are unprecedented in Mn chemistry. The [Mn(III)(9)(μ(3)-O)(7)](13+) core of 3 also contains two body-fused Mn(4) butterfly units, but they are linked to the remaining Mn atoms in a different manner than in 1. Solid-state direct current (dc) and/or alternating current (ac) magnetic susceptibility data established S = (15)/(2), S = 2, and S = 1 ground states for 1·MeCN, 2·(1)/(4)MeCN, and 3, respectively. The ac susceptibility data also revealed nonzero, frequency-dependent out-of-phase (χ″(M)) signals for 1·MeCN at temperatures below 3 K, suggesting possible single-molecule magnet behavior, which was confirmed by single-crystal magnetization vs dc field scans that exhibited hysteresis loops. The combined work thus demonstrates the continuing potential of comproportionation reactions for isolating high oxidation state Mn(x) clusters, and the sensitivity of the product identity to minor changes in the reaction conditions.

Synthesis, Structure, and Spectroscopic and Magnetic Characterization of [Mn12O12(O2CCH2But)16(MeOH)4]·MeOH, a Mn12 Single-Molecule Magnet with True Axial Symmetry

The synthesis and properties are reported of a rare example of a Mn(12) single-molecule magnet (SMM) in truly axial symmetry (tetragonal, I4). [Mn(12)O(12)(O(2)CCH(2)Bu(t))(16)(MeOH)(4)]·MeOH (3·MeOH) was synthesized by carboxylate substitution on [Mn(12)O(12)(O(2)CMe)(16)(H(2)O)(4)]·2MeCO(2)H·4H(2)O (1). The complex was found to possess an S = 10 ground state, as is typical for the Mn(12) family, and displayed both frequency-dependent out-of-phase AC susceptibility signals and hysteresis loops in single-crystal magnetization vs DC field sweeps. The loops also exhibited quantum tunneling of magnetization steps at periodic field values. Single-crystal, high-frequency electron paramagnetic resonance spectra on 3·MeOH using frequencies up to 360 GHz revealed perceptibly sharper signals than for 1. Moreover, careful studies as a function of the magnetic field orientation did not reveal any satellite peaks, as observed for 1, suggesting that the crystals of 3 are homogeneous and do not contain multiple Mn(12) environments. In the single-crystal (55)Mn NMR spectrum in zero applied field, three well-resolved peaks were observed, which yielded hyperfine and quadrupole splitting at three distinct sites. However, observation of a slight asymmetry in the Mn(4+) peak was detectable, suggesting a possible decrease in the local symmetry of the Mn(4+) site. Spin-lattice (T(1)) relaxation studies were performed on single crystals of 3·MeOH down to 400 mK in an effort to approach the quantum tunneling regime, and fitting of the data using multiple functions was employed. The present work and other recent studies continue to emphasize that the new generation of truly high-symmetry Mn(12) complexes are better models for thorough investigation of the physical properties of SMMs than their predecessors such as 1.

Cationic Mn4 Single-Molecule Magnet with a Sterically Isolated Core

The synthesis, structure, and magnetic properties of a ligand-modified Mn(4) dicubane single-molecule magnet (SMM), [Mn(4)(Bet)(4)(mdea)(2)(mdeaH)(2)](BPh(4))(4), are presented, where the cationic SMM units are significantly separated from neighboring molecules in the crystal lattice. There are no cocrystallized solvate molecules, making it an ideal candidate for single-crystal magnetization hysteresis and high-frequency electron paramagnetic resonance studies. Increased control over intermolecular interactions in such materials is a crucial factor in the future application of SMMs.

The search for cobalt single-molecule magnets: A disk-like Co IIICo II6 cluster with a ligand derived from a novel transformation of 2-acetylpyridine

The initial employment of 2-acetylpyridine, (py)(Me)CO, in Co cluster chemistry is reported, and the synthesis, crystal structure, and full magnetic study of [Co 7(OH) 6(L) 6](ClO 4) 3·1.6H 2O ( 1·1.6H 2O) are described; L − is the anion of 2-(pyridine-2-yl)pentane-2-ol-4-one, (py)(Me)C(CH 2COCH 3)(O) −, formed in situ through a crossed-aldol reaction in acetone under strongly basic conditions. The reaction of Co(ClO 4) 2·6H 2O, (py)(Me)CO and NBu n 4OMe (1:1:1.2) in acetone at room temperature under aerobic conditions affords 1·1.6H 2O in 35% yield. The mixed-valent cation possesses a wheel-shaped (or disk-like) structural motif comprising a central octahedral Co III atom linked to six peripheral distorted octahedral Co II atoms by six μ 3-ΟΗ − groups; the six Co II atoms on the rim are held together by six η 1:η 1:η 1:μ 2·L − ligands and the oxygen atoms of the hydroxo groups. Variable-temperature, solid-state dc and ac magnetic susceptibility studies were carried out on 1. The dc magnetic study of 1 shows a decline in the product χ Μ T with decreasing T. The observation of out-of phase ( χ″ Μ) ac susceptibility signals below ∼4 K suggests that the Co IIICo II 6 complex may be a single molecule magnet, and this was confirmed by single-crystal magnetization vs. dc field sweeps down to 0.04 K that exhibited hysteresis. The study reveals that each complex cation is a weak single-molecule magnet, but that there are also intermolecular interactions (also confirmed crystallographically) to create a 3D ordered lattice; this still gives some hysteresis at 5 K.

119Sn Mössbauer spectroscopy study of the magnetic properties of the HfFe 6Ge 6-type compounds: SmMn 6Sn 4Ge 2 and GdMn 6Sn 4Ge 2

The HfFe 6Ge 6-type compound SmMn 6Sn 4Ge 2 has been studied by single-crystal magnetisation and 119Sn Mössbauer spectroscopy. The compound orders ferromagnetically at T c = 420 K and displays an easy-axis anisotropy from T c to T SR = 130 K. Below T SR, both magnetisation and 119Sn Mössbauer spectroscopy measurements indicate a deviation from the [0 0 1] direction and the presence of easy-cone anisotropy. The angle of the moments with respect to the [0 0 1] direction is estimated to 26–31° from Mössbauer spectroscopy results, in good accordance with the magnetisation results. The isotypic compounds GdMn 6Sn 4Ge 2 and GdMn 6Sn 6 studied by 119Sn Mössbauer spectroscopy display easy plane anisotropy in the whole temperature range 300–4.2 K. The anisotropy behaviours of the LMn 6Sn 4Ge 2 compounds are discussed and the coexistence of easy cone anisotropy for both the SmMn 6Sn 4Ge 2 and HoMn 6Sn 4Ge 2 suggests the play of a positive second-order anisotropy constant of the Mn sublattice.

Combining Azide, Carboxylate, and 2-Pyridyloximate Ligands in Transition-Metal Chemistry: Ferromagnetic NiII5 Clusters with a Bowtie Skeleton

The combined use of the anion of phenyl(2-pyridyl)ketone oxime (ppko(-)) and azides (N(3)(-)) in nickel(II) carboxylate chemistry has afforded two new Ni(II)(5) clusters, [Ni(5)(O(2)CR')(2)(N(3))(4)(ppko)(4)(MeOH)(4)] [R' = H (1), Me (2)]. The structurally unprecedented {Ni(5)(μ-N(3))(2)(μ(3)-N(3))(2)}(6+) cores of the two clusters are almost identical and contain the five Ni(II) atoms in a bowtie topology. Two N(3)(-) ions are end-on doubly bridging and the other two ions end-on triply bridging. The end-on μ(3)-N(3)(-) groups link the central Ni(II) atoms with the two peripheral metal ions on either side of the molecule, while the Ni···Ni bases of the triangles are each bridged by one end-on μ-N(3)(-) group. Variable-temperature, solid-state direct- (dc) and alternating-current (ac) magnetic susceptibility, and magnetization studies at 2.0 K were carried out on both complexes. The data indicate an overall ferromagnetic behavior and an S = 5 ground state for both compounds. The ac susceptibility studies on 1 reveal nonzero, frequency-dependent out-of-phase (χ(M)") signals at temperatures below ~3.5 K; complex 2 reveals no χ(M)" signals. However, single-crystal magnetization versus dc field scans at variable temperatures and variable sweep rates down to 0.04 K on 1 reveal no noticeable hysteresis loops, except very minor ones at 0.04 K assignable to weak intermolecular interactions propagated by nonclassical hydrogen bonds.

Ba-hexaferrite quasi-single crystals prepared with single-domain crystallites fabrication, structural characterization and magnetic properties

As a good gyromagnetic material for the applications in microwave and millimeter wave devices, Ba-hexaferrite quasi-single crystals have been successfully fabricated by using its nanosized single-domain crystallites as the starting materials via press-forming in magnetic field and sintering with minor liquid phase participation at 1280 °C for 10 h. The material is characterized by a highly densified and laminar fracture microtexture with a grain orientation degree of as high as 99% and shows a single-crystal magnetization behavior featured by 4 πMs=4654 Gs, H a =16800 Oe and H c =120 Oe, suggesting a narrower ferromagnetic resonance linewidth Δ H than the counterpart fabricated by solid-state sintering technique.

High Nuclearity Single-Molecule Magnets: a Mixed-Valence Mn26 Cluster Containing the Di-2-pyridylketone Diolate Dianion

The employment of the dianion (dpkd(2-)) of the gem-diol form of di-2-pyridylketone (dpk) as a tetradentate chelate in manganese chemistry is reported, and the synthesis, crystal structure, and magnetochemical characterization of [Mn26O16(OMe)12(dpkd)12(MeOH)6](OH)6 x solv (3 x solv) are described. The reaction of Mn(ClO4)2 x 6 H2O, dpk, NaOMe, and NEt3 (2:1:4:2) in MeCN/MeOH affords complex 3, which possesses a rare metal topology and is mixed-valence (4 Mn(II), 22 Mn(III)). The complicated [Mn26(mu4-O)10(mu3-O)6(mu3-OMe)12(mu-OR)12](18+) core of 3 consists of an internal Mn(III)16 cage of adjacent Mn4 tetrahedra surrounded by an external Mn(II)4Mn(III)6 shell. The latter is held together by the alkoxide arms of twelve eta(1):eta(2):eta(1):eta(1):mu3 dpkd(2-) groups. Variable-temperature, solid-state direct current (dc), and alternating current (ac) magnetization studies were carried out on 3 in the 1.8-300 K range. Complex 3 is predominantly antiferromagnetically coupled with a resulting S = 6 ground state, a conclusion confirmed by the in-phase (chi'(M)) ac susceptibility data. The observation of out-of-phase (chi''(M)) ac susceptibility signals suggested that 3 might be a single-molecule magnet, and this was confirmed by single-crystal magnetization vs dc field sweeps that exhibited hysteresis, the diagnostic property of a magnet. Combined ac chi''(M) and magnetization decay vs time data collected below 1.1 K were used to construct an Arrhenius plot; the fit of the thermally activated region above approximately 0.1 K gave U(eff) = 30 K, where U(eff) is the effective relaxation barrier. At lower temperatures, the complex exhibits temperature-independent relaxation, characteristic of ground-state quantum tunneling of magnetization between the lowest-lying M(s) = +/-6 levels. The combined work demonstrates the ligating flexibility of dipyridyl-diolate chelates and their usefulness in the synthesis of polynuclear Mn(x) clusters with interesting magnetic properties, without requiring the co-presence of carboxylate ligands.