A six-coordinate ytterbium complex exhibiting easy-plane anisotropy and field-induced single-ion magnet behavior

The field-induced blockage of magnetization behavior was first observed in an Yb(III)-based molecule with a trigonally distorted octahedral coordination environment. Ab initio calculations and micro-SQUID measurements were performed to demonstrate the exhibition of easy-plane anisotropy, suggesting the investigated complex is the first pure lanthanide field-induced single-ion magnet (field-induced SIM) of this type. Furthermore, we found the relaxation time obeys a power law instead of an exponential law, indicating that the relaxation process should be involved a direct process rather than an Orbach process.     

Slow magnetic relaxation in a pseudotetrahedral cobalt(II) complex with easy-plane anisotropy

A pseudotetrahedral cobalt(II) complex with a positive axial zero-field splitting parameter of D = 12.7 cm(-1), as determined by high-field EPR spectroscopy, is shown to exhibit slow magnetic relaxation under an applied dc field.     

A co-crystal of polyoxometalates exhibiting single-molecule magnet behavior: the structural origin of a large magnetic anisotropy

A polyoxometalate-based {Mn(III)(3)Mn(IV)} single-molecule magnet exhibits a large axial anisotropy (D = -0.86 cm(-1)) resulting from a near-parallel alignment of Jahn-Teller axes. Its rigorous three-fold symmetry (i.e. rhombicity E→ 0) and increased intercluster separation via co-crystallization effectively hamper quantum tunnelling of the magnetization.     

A high anisotropy barrier in a sulfur-bridged organodysprosium single-molecule magnet

The sulfur-bridged dimers [{Cp'(2)Ln(μ-SSiPh(3))}(2)] (Ln=Gd (1), Dy (2); Cp'=η(5)-C(5)H(4)Me) were synthesized by the transmetalation reactions between [Cp'(3)Ln] and Ph(3)SiSLi. Compound 2 is a single-molecule magnet with slow relaxation of magnetization up to 40 K and an anisotropy barrier of U(eff) =133 cm(-1). Insight into the SMM properties of 2 and closely related SMMs has been obtained using ab initio calculations.     

Coexistence of magnetization relaxation and dielectric relaxation in a single-chain magnet

A novel single-chain magnet, [MnIII3O(Meppz)3(EtOH)4(OAc)] (1), has been successfully synthesized from a secondary building block [MnIII3O(Meppz)3(EtOH)5Cl] (2) with an S = 1 ground state. SCM 1 exhibits both magnetization relaxation and dielectric relaxation properties.     

Modulation of ionic arrangement in polar magnet by chemical pressure

The similarity of local structure-connection pattern and volumetrically compressive strain between host and guest phases can be used to stabilize heteroid metastable matter and tune the local structure and properties. Here a series of metastable ABO₃ (A = Mn; B = Mn_0.5Mo_0.5, Mn_1/3Ta_2/3, and Mn_0.5Ta_0.5) were trapped in LiTaO₃ to form solid-solutions, where the difference of solid solubility limit reveals the barrier of size effect on chemical pressure. All samples show antiferromagnetic characters, in which the (LiTaO₃)_1-x-[Mn(Mn_0.5Mo_0.5)O₃]_x series exhibit more complex magnetic and dielectric behaviors with the increasing of metastable guest phase, stemming from the complex interactive mechanism between Mn²⁺ and Mo⁶⁺. The cell parameter variation of (LiTaO₃)_1-z-[Mn(Mn_0.5Ta_0.5)O₃]_z shows a more regularly changing tendency, on account of the smallest size barrier. These findings show that chemical pressure can effectively stimulate the physical pressure to intercept and modulate a metastable phase at atomic-scale by compressibility effect between like structures at ambient pressure.     

Intermolecular contact-tuned magnetic nature in one-dimensional 3d-5d bimetallic systems: from a metamagnet to a single-chain magnet

Assembling [W(CN) 6(bpy)] (-) and magnetic anisotropic Mn Schiff bases produced two Mn (III)(3d)-W (V)(5d) bimetallic chains. Modulation of the types and degrees of interchain pi-pi interactions in the one-dimensional coordination polymers leads to the variation of the magnetic behavior from a metamagnetic character to a single-chain magnet property.     

Synthesis and characterization of a Mn22 single-molecule magnet and a [Mn22]n single-chain magnet

The reactions of [Mn12O12(O2CEt)16(H2O)4] with phenylphosphinic acid (PhHPO2H) in MeCN and MeCN/CH2Cl2 have led to isolation of [Mn22O12(O2CEt)22(O3PPh)8(H2O)8] (2) and [Mn22O12(O2CEt)20(O3PPh)8(O2PPhH)2(H2O)8]n (3), respectively, both containing PhPO3(2-) groups from in situ oxidation of PhHPO(2)(-). Complex 2 is molecular and consists of two Mn9 subunits linked by four additional Mn atoms. Complex 3 contains almost identical Mn22 units as 2, but they are linked into a one-dimensional chain structure. The Mn22 unit in both compounds is mixed-valence Mn(III)18, Mn(II)4. Solid-state, variable-temperature dc magnetic susceptibility and magnetization measurements were performed on vacuum-dried samples of 2 and 3, indicating dominant antiferromagnetic interactions. A good fit of low-temperature magnetization data for 2 could not be obtained because of problems associated with low-lying excited states, as expected for a high nuclearity complex containing Mn(II) atoms. An approximate fit using only data collected in small applied fields indicated an S = 7 or 8 ground state for 2. Solid-state ac susceptibility data established that the true ground state of 2 is S = 7 and that the connected Mn22 units of 3 are ferromagnetically coupled. Both 2 and 3 displayed weak out-of-phase ac signals indicative of slow magnetization relaxation. Single-crystal magnetization versus applied dc field scans exhibited hysteresis loops for both compounds, establishing them as new single-molecule and single-chain magnets, respectively. Complex 2 also showed steps in its hysteresis loops characteristic of quantum tunneling of magnetization, the highest nuclearity molecule to show such QTM steps. Arrhenius plots constructed from dc magnetization versus time decay plots gave effective barriers to magnetization relaxation (U(eff)) of 6 and 11 cm(-1) for 2 and 3, respectively.     

Slow magnetic relaxation induced by a large transverse zero-field splitting in a Mn(II)Re(IV)(CN)2 single-chain magnet

The model compounds (NBu(4))(2)[ReCl(4)(CN)(2)] (1), (DMF)(4)ZnReCl(4)(CN)(2) (2), and [(PY5Me(2))(2)Mn(2)ReCl(4)(CN)(2)](PF(6))(2) (3) have been synthesized to probe the origin of the magnetic anisotropy barrier in the one-dimensional coordination solid (DMF)(4)MnReCl(4)(CN)(2) (4). High-field electron paramagnetic resonance spectroscopy reveals the presence of an easy-plane anisotropy (D > 0) with a significant transverse component, E, in compounds 1-3. These findings indicate that the onset of one-dimensional spin correlations within the chain compound 4 leads to a suppression of quantum tunneling of the magnetization within the easy plane, resulting in magnetic bistability and slow relaxation behavior. Within this picture, it is the transverse E term associated with the Re(IV) centers that determines the easy axis and the anisotropy energy scale associated with the relaxation barrier. The results demonstrate for the first time that slow magnetic relaxation can be achieved through optimization of the transverse anisotropy associated with magnetic ions that possess easy-plane anisotropy, thus providing a new direction in the design of single-molecule and single-chain magnets.     

Periodic deformations induced by a magnetic field in planar twisted nematic layers

Magnetic field-induced spatially periodic deformations of planar nematic layers twisted by an angle Φ were investigated numerically. Chiral nematics with pitches compatible with the twist angle and non-chiral nematics twisted by Φ ≤π/2 were considered. Two different modes of deformation, taking the form of stripes, were found: the so called Mode X, with periodicity parallel to the mid-plane director in the undisturbed structure, and Mode Y with periodicity perpendicular to the mid-plane director. The static director distributions were calculated for various magnetic field strengths, twist angles and elastic parameters. The influence of surface tilt was also investigated. Mode X appeared for sufficiently large Φ and was possible in nematics with typical elastic properties. Mode Y appeared provided that the k₂₂/k₁₁ elastic constant ratio and the twist angle Φ were sufficiently small. Both modes arose from the undistorted state when the magnetic field exceeded a threshold value. The spatial period of the patterns increased with field strength. At high field, regions with almost homogeneous deformation arose in the two halves of each stripe. Their width and, simultaneously, the spatial period diverged to infinity at some critical field. This divergence corresponds to the transition to a homogeneously deformed state. Diagrams were constructed showing the ranges of parameters favouring the periodic distortions.     

Periodic deformations induced by a magnetic field in planar twisted nematic layers

Magnetic field-induced spatially periodic deformations of planar nematic layers twisted by an angle Φ were investigated numerically. Chiral nematics with pitches compatible with the twist angle and non-chiral nematics twisted by Φ ? π/2 were considered. Two different modes of deformation, taking the form of stripes, were found: the so called Mode X, with periodicity parallel to the mid-plane director in the undisturbed structure, and Mode Y with periodicity perpendicular to the mid-plane director. The static director distributions were calculated for various magnetic field strengths, twist angles and elastic parameters. The influence of surface tilt was also investigated. Mode X appeared for sufficiently large Φ and was possible in nematics with typical elastic properties. Mode Y appeared provided that the k ₂₂/k ₁₁ elastic constant ratio and the twist angle Φ were sufficiently small. Both modes arose from the undistorted state when the magnetic field exceeded a threshold value. The spatial period of the patterns increased with field strength. At high field, regions with almost homogeneous deformation arose in the two halves of each stripe. Their width and, simultaneously, the spatial period diverged to infinity at some critical field. This divergence corresponds to the transition to a homogeneously deformed state. Diagrams were constructed showing the ranges of parameters favouring the periodic distortions.     

Hydration of gas-phase ions formed by electrospray ionization

The hydration of gas-phase ions produced by electrospray ionization was investigated. Evidence that the hydrated ions are formed by two mechanisms is presented. First, solvent condensation during the expansion inside the electrospray source clearly occurs. Second, some solvent evaporation from more extensively solvated ions or droplets is apparent. To the extent that these highly solvated ions have solution-phase structures, then the final isolated gas-phase structure of the ion will be determined by the solvent evaporation process. This process was investigated for hydrated gramicidin S in a Fourier-transform mass spectrometer. Unimolecular dissociation rate constants of isolated gramicidin S ions with between 2 and 14 associated water molecules were measured. These rate constants increased from 16 to 230 s-1 with increasing hydration, with smaller values corresponding to magic numbers.     

Ligand effects toward the modulation of magnetic anisotropy and design of magnetic systems with desired anisotropy characteristics

Magnetic anisotropy of a set of octahedral Cr(III) complexes is studied theoretically. The magnetic anisotropy is quantified in terms of zero-field splitting (ZFS) parameter D, which appeared sensitive toward ligand substitution. The increased π-donation capacity of the ligand enhances the magnetic anisotropy of the complexes. The axial π-donor ligand of a complex is found to produce an easy-plane type (D > 0) magnetic anisotropy, while the replacement of the axial ligands with π-acceptors entails the inversion of magnetic anisotropy into the easy-axis type (D < 0). This observation enables one to fabricate a single molecule magnet for which easy-axis type magnetic anisotropy is an indispensable criterion. The equatorial ligands are also found to play a role in tuning the magnetic anisotropy. The magnetic anisotropy property is also correlated with the nonlinear optical (NLO) response. The value of the first hyperpolarizability varies proportionately with the magnitude of the ZFS parameter. Finally, it has also been shown that a rational design of simple octahedral complexes with desired anisotropy characteristics is possible through the proper ligand selection.     

Homochiral frameworks formed by reactions of lanthanide ions with a chiral antimony tartrate secondary building unit

A chiral cluster compound, dipotassium bis(μ-tartrato)diantimony(III), K(2)Sb(2)L(2) (H(4)L = L-tartaric acid), was used as a secondary building unit to react with lanthanide ions. Three series of homochiral coordination compounds were obtained: 0D [La(H(2)L)(H(2)O)(4)](2)[Sb(2)L(2)]·7H(2)O (0D-La), 1D Ln(Sb(2)L(2))(H(2)O)(5)(NO(3))·H(2)O (1D-Ln) (Ln = La-Lu or Y, expect Pm), 2D(I) [(Ln(H(2)O)(5))(2)(Sb(2)L(2))(3)]·5H(2)O (2D(I)-Ln) (Ln = La, Ce, Pr), and 2D(II) [(La(H(2)O)(5))(2)(Sb(2)L(2))(3)]·6H(2)O (2D(II)-La). Single-crystal X-ray diffraction studies indicated that 0D-La crystallizes in space group P1, and the structure contains isolated Sb(2)L(2)(2-) units located between chains of composition La(H(2)L)(H(2)O)(4). The series of 1D-Ln compounds is isostructural and crystallizes in space group P2(1)2(1)2(1). In the structure, Sb(2)L(2)(2-) units are coordinated to two Ln ions by two out of the four free tartrate oxygen atoms to form a linear chain. To the best of our knowledge, this is the first example of a homochiral structure that can be formed for the whole lanthanide series. In the 2D(I)-Ln structure series, which crystallizes in space group P2(1), the Sb(2)L(2)(2-) units have two distinct coordination modes: one is the same as that found in the 1D structure, while in the other all four free tartrate oxygen atoms are coordinated to four Ln ions in a very distorted tetrahedral arrangement. The connectivity between Sb(2)L(2)(2-) secondary units and LnO(9) polyhedra gives rise to infinite layers. 2D(II) [(La(H(2)O)(5))(2)(Sb(2)L(2))(3)]·6H(2)O, which crystallizes in space group C2, has a similar network to the 2D(I)-Ln compounds. The trends in lattice parameters, bond lengths, and ionic radii in the 1D-Ln series were analyzed to show the effect of the lanthanide contraction.     

A Mn(III)2Ni(II) single-chain magnet separated by a thick isolating network of BPh4- anions

The assembly reaction of a Mn(III) salen-type dimeric complex, [MnIII2(saltmen)2(H2O)2](ClO4)2 (saltmen2- = N,N'-(1,1,2,2-tetramethylethylene)bis(salycylideneiminate)), and a Ni(II) oximato complex, [Ni(II)(pao)2(phen)] (pao- = pyridine-2-aldoximate; phen = 1,10-phenanthroline), in the presence of NaBPh4 yielded a heterometallic chain of [MnIII2(saltmen)2NiI)(pao)2(phen)](BPh4)2 (Mn2Ni-BPh4) having a [-Mn(III)-ON-Ni(II)-NO-Mn(III)-(OPh)2-] repeating unit surrounded by a "zeolite-like" network of BPh4- anions. Thanks to such bulky ion-walls, each chain is not only structurally separated with a nearest inter-chain metalmetal distance of 14.4 A (MnNi) but also magnetically extremely well isolated. This magnetic isolation and the ferromagnetic interactions between S = 3 anisotropic units constituting the chain play key roles that induce single-chain magnet behavior in this system.     

Rotation in a magnetic field of nematic liquid crystalline samples with a negative anisotropy of their magnetic susceptibility

The behaviour of the mesophase directors when a sample with a negative anisotropy Deltachi in the magnetic susceptibility is rotated at a speed omega in a magnetic field B0 about an axis inclined at an angle beta is investigated by deuterium NMR spectroscopy. There are combinations of beta and omega which lead to the directors aligning along the spinning axis (stable region), and other combinations where the directors are either unaffected by the rotation, or have a timedependent distribution (unstable region). These two regions are separated by a line (the q line) whose position depends on beta and omegac DeltachiB02/2mu0gamma1, where gamma1 is a twist viscosity coefficient. Experiments on 4-n-propyl-4-cyanobicyclohexane (CCH3) are used to demonstrate how the q line, and hence omegac may be determined. Combining this result with a measurement of the anisotropy in the magnetic susceptibility, Deltachi, yields a value for gamma1.