Intrachain Antiferromagnetic Coupling Research Articles

Influence of Cr-ion substitution on the magnetization and dielectric properties of the frustrated Ca3CoMnO6 compound

The Cr-doped Ca3CoMn1-xCrxO6 (x=0, 0.05, 0.1, 0.15) polycrystalline samples were prepared using a modified sol-gel method. The structural, magnetic and dielectric properties were systemically investigated. With increasing Cr3+-doping level, the partial Co2+ ions change to Co3+, leading to a decreased lattice volume. Correspondingly, the length of the short-range magnetic correlation is inhibited and a faster dynamic behavior in time dependent magnetization is found. At the benefit of the magnetic structural changes with the introduction of Cr3+ ions, the relaxor degree of the ferroelectric transition that induced by the exchange striction becomes lower, while the activation energy of the frozen polar-nanoregions increases. The replacement of Mn4+ by Cr3+ also leads to a reduced intra-chain antiferromagnetic coupling and the emergence of Co3+-Co3+ ferromagnetic interaction. As consequence, the Curie-Weiss temperature (θ) increases monotonously. The variation in dielectric permittivity with magnetic field confirms the existence of large magnetodielectric coupling in the Ca3CoMn1-xCrxO6 (0 ​≤ ​x ​≤ ​0.15) samples. Especially for the x ​= ​0.15 sample, the permittivity changes by about 7% under the magnetic field of H=4 ​T.

Exchange coupling in a thiocyanato-bridged copper(II) chain: Computational approach to magnetostructural correlations

In this article we report the synthesis and magneto-structural characterization of two new copper(II) compounds with thiocyanato and methyl(2-pyridil) ketone oxime (mpkOH), namely [Cu(NCS)(mpkO)(mpkOH)] (1) and [Cu(µ-NCS)(NCS)(mpkOH)]n (2). Compound 1 is a mononuclear complex that crystallizes as discrete units. Conversely, compound 2 is a single equatorial-axial end-to-end thiocyanato bridged polymeric chain of Cu(II) with the oxime as a co-ligand. The coordination geometry around the Cu(II) centers is distorted square pyramidal for 1 and 2. The magnetic susceptibility data for 2 reveal weak intrachain antiferromagnetic coupling, with J value −0.74(3) cm−1 and g = 2.10(1). The application of computational tools to a binuclear model of 2 allowed us to unveil the structural basis that modulates the magnetic behavior of this type of thiocyanato-bridged Cu(II) chains. The results suggest that although small values of J are expected, the strongest ferromagnetic interactions can be obtained by including co-ligands that trigger a squared-based pyramidal-to-trigonal bipyramidal distortion of the coordination polyhedra.

Intrachain collinear magnetism and interchain magnetic phases in Cr3As3−K -based materials

We perform a comparative study of the KCr3As3 and the K2Cr3As3 quasi 1D compounds, and show that the strong interplay between the lattice and the spin degrees of freedom promotes a new collinear ferrimagnetic ground state within the chains in presence of intrachain antiferromagnetic couplings. We propose that the interchain antiferromagnetic coupling in KCr3As3 plays a crucial role for the experimentally observed spin-glass phase with low critical temperature. In the same region of the parameter space, we predict K2Cr3As3 to be non-magnetic but on the verge of the magnetism, sustaining interchain ferromagnetic spin fluctuations while the intrachain spin fluctuations are antiferromagnetic.

Ferrimagnetic Fe(IV)-Mn(II) staircase chain constructed from Fe(IV) building block

A novel manganese compound with Fe(IV) building block has been synthesized and characterized by single-crystal diffraction analysis, which presents of a 1D staircase chain structure. The adjacent staircase chains are expended into a 2D layer through π-π interaction between the terminal oxalyl groups. Furthermore, the 2D layers are connected to form a 3D supramolecular framework by rich hydrogen bonds. Low-temperature magnetic measurements reveal that intrachain antiferromagnetic couplings dominates through the FeIV-oxamido-MnII pathways, concomitantly with a typical ferrimagnetic behavior.

Electronic structures of quasi-one-dimensional cuprate superconductors Ba2CuO3+δ

An intact CuO$_2$ plane is widely believed to be a prerequisite for the high-$T_c$ superconductivity in cuprate superconductors. However, an exception may exist in the superconducting Ba$_2$CuO$_{3+\delta}$ materials where CuO chains play a more important role. From first-principles density functional theory calculations, we have studied the electronic and magnetic structures of Ba$_2$CuO$_{3+\delta}$. The stoichiometric Ba$_2$CuO$_3$ and Ba$_2$CuO$_4$ contain quasi-one-dimensional CuO chains and intact two-dimensional CuO$_2$ planes, respectively. In comparison with the nonmagnetic metal Ba$_2$CuO$_4$, Ba$_2$CuO$_3$ is found to be an antiferromagnetic (AFM) Mott insulator. It possesses a nearest-neighbor intra-chain antiferromagnetic (AFM) coupling and a weak inter-chain interaction, and its lowest unoccupied band and highest occupied band are contributed by Cu 3$d_{b^2-c^2}$-orbital (or $d_{x^2-y^2}$-orbital if we denote the $bc$-plane as the $xy$-plane) and O 2$p$-orbitals, respectively. Total energy calculations indicate that the oxygen vacancies in Ba$_2$CuO$_{3+\delta}$ prefer to reside in the planar sites rather than the apical oxygens in the CuO chains, in agreement with the experimental observation. Furthermore, we find that the magnetic frustrations or spin fluctuations can be effectively induced by moderate charge doping. This suggests that the superconducting pairing in oxygen-enriched Ba$_2$CuO$_{3+\delta}$ or oxygen-deficient Ba$_2$CuO$_{4-\delta}$ is likely to be mainly driven by the AFM fluctuations within CuO chains.

Thermally and Magnetically Robust Triplet Ground State Diradical.

High spin ( S = 1) organic diradicals may offer enhanced properties with respect to several emerging technologies, but typically exhibit low singlet triplet energy gaps and possess limited thermal stability. We report triplet ground state diradical 2 with a large singlet-triplet energy gap, Δ EST ≥ 1.7 kcal mol-1, leading to nearly exclusive population of triplet ground state at room temperature, and good thermal stability with onset of decomposition at ∼160 °C under inert atmosphere. Magnetic properties of 2 and the previously prepared diradical 1 are characterized by SQUID magnetometry of polycrystalline powders, in polystyrene glass, and in other matrices. Polycrystalline diradical 2 forms a novel one-dimensional (1D) spin-1 ( S = 1) chain of organic radicals with intrachain antiferromagnetic coupling of J'/ k = -14 K, which is associated with the N···N and N···O intermolecular contacts. The intrachain antiferromagnetic coupling in 2 is by far strongest among all studied 1D S = 1 chains of organic radicals, which also makes 1D S = 1 chains of 2 most isotropic, and therefore an excellent system for studies of low-dimensional magnetism. In polystyrene glass and in frozen benzene or dibutyl phthalate solution, both 1 and 2 are monomeric. Diradical 2 is thermally robust and is evaporated under ultrahigh vacuum to form thin films of intact diradicals on silicon substrate, as demonstrated by X-ray photoelectron spectroscopy. Based on C-K NEXAFS spectra and AFM images of the ∼1.5 nm thick films, the diradical molecules form islands on the substrate with molecules stacked approximately along the crystallographic a-axis. The films are stable under ultrahigh vacuum for at least 60 h but show signs of decomposition when exposed to ambient conditions for 7 h.

S = 1 Tetraazacyclophane Diradical Dication with Robust Stability: A Case of Low-Temperature One-Dimensional Antiferromagnetic Chain

One-dimensional (1D) spin-1 ( S = 1) chain of organic radicals with low local magnetic anisotropy may provide a better understanding of the low-dimensional magnetism. We report solid-state studies, including single crystal X-ray crystallography, of air-stable tetraazacyclophane diradical dication salt 12·2+·2[Al(OC(CF3)2CH3)4]- with a triplet ground state (Δ EST ≈ 0.5 kcal mol-1). The magnetic behavior for 12·2+ at low temperature is best modeled by 1D spin S = 1 Heisenberg chain with intrachain antiferromagnetic coupling of J'/ k = -5.4 K, which is associated with the interaryl C···C contacts, including π-π interactions. Zero-field splitting value, | D/ hc| ≈ 5.6 × 10-3 cm-1, for 12·2+ is rather small; thus, the 1D chains are characterized by the high degree of isotropicity | D/2 J'| ≈ 7.5 × 10-4. The diradical dication salt possesses extraordinary stability with onset of decomposition at temperature of about 180 °C (∼450 K), based on thermogravimetric analysis and EPR spectroscopy.

Seven-coordinate tetraoxolate complexes

The reaction of TPypA (tris(2-pyridylmethyl)amine) and Fe(BF4)2 and sodium nitraniIate (Na21NO2) or Mn(O2CMe)2 with chloranilic acid (H21Cl) respectively forms [FeIII(TPyA)1NO2]2O and MnII(TPyA)1Cl, respectively. The structures of these 7-coordinate compounds have been determined. The former is a dinuclear FeIII compound possessing equivalent Fe(III) sites, and the latter forms a 1-D zigzag chain based upon the two bridging 1NO22− ions. The isomer shift and quadrupole splitting of the 57Fe Mössbauer spectra of [Fe(TPyA)1NO2]2O are consistent binuclear seven-coordinate high-spin FeIII state. Below 35 K a single quadrupole doublet split onto two doublets of equal intensities and equal isomer shifts as a result of structural non-equivalency of two iron sites within a dimer. The magnetic properties of [FeIII(TPyA)1NO2]2O can be fit the a homonuclear S = 5/2 ± 5/2 dinuclear spin model with strong intradimer antiferromagnetic coupling of J/kB = −146 K (−101 cm−1) and g = 2.00, and interdimer coupling of θ = −5 K (H = −2JSa·Sb). MnII(TPyA)1Cl can be fit the a homonuclear S = 5/2 1-D Fisher chain expression with weak intrachain antiferromagnetic coupling with J/kB = −0.33 K (−0.23 cm−1) and g = 2.06.

Antiferromagnetic spin chain behavior and a transition to 3D magnetic order in Cu(D,L-alanine)2: Roles of H-bonds

We study the spin chain behavior, a transition to 3D magnetic order and the magnitudes of the exchange interactions for the metal-amino acid complex Cu(D,L-alanine)2∙H2O, a model compound to investigate exchange couplings supported by chemical paths characteristic of biomolecules. Thermal and magnetic data were obtained as a function of temperature (T) and magnetic field (B0). The magnetic contribution to the specific heat, measured between 0.48 and 30 K, displays above 1.8 K a 1D spin-chain behavior that can be fitted with an intrachain antiferromagnetic (AFM) exchange coupling constant 2J0=(−2.12±0.08) cm−1 (defined as ℋex(i,i+1)=−2J0Si⋅Si+1), between neighbor coppers at 4.49 Å along chains connected by non-covalent and H-bonds. We also observe a narrow specific heat peak at 0.89 K indicating a phase transition to a 3D magnetically ordered phase. Magnetization curves at fixed T=2, 4 and 7 K with B0 between 0 and 9 T, and at T between 2 and 300 K with several fixed values of B0 were globally fitted by an intrachain AFM exchange coupling constant 2J0=(−2.27±0.02) cm−1 and g=2.091±0.005. Interchain interactions J1 between coppers in neighbor chains connected through long chemical paths with total length of 9.51 Å cannot be estimated from magnetization curves. However, observation of the phase transition in the specific heat data allows estimating the range 0.1≤|2J1|≤0.4 cm−1, covering the predictions of various approximations. We analyze the magnitudes of 2J0 and 2J1 in terms of the structure of the corresponding chemical paths. The main contribution in supporting the intrachain interaction is assigned to H-bonds while the interchain interactions are supported by paths containing H-bonds and carboxylate bridges, with the role of the H-bonds being predominant. We compare the obtained intrachain coupling with studies of compounds showing similar behavior and discuss the validity of the approximations allowing to calculate the interchain interactions.

Low dimensional magnetic assemblies based on MnIII(Schiff base) and/or Mer-tricyanidoferrate building blocks: Syntheses, crystal structures and magnetic properties

Four new MnIII(Schiff base) and/or [FeIII(L)(CN)3]− (L=mpzcq, qcq) based complexes, PPh4[FeIII(mqzcq)(CN)3]·4H2O (1), {[MnIII(5-CH3O-salen)(H2O)]2[FeIII(mqzcq)(CN)3]2}·2H2O (2), {[MnIII(5-CH3-salen)][FeIII(mqzcq)(CN)3]}·H2O·CH3CN (3) and {[MnIII(4-CH3O-salcy)] [FeIII(qcq)(CN)3]}·2CH3CN (4) (mqzcq=8-(5-methylpyrazine-2-carboxamido)quinoline; qcq=8-(2-quinoline-2-carboxamido)quinoline; salen=N,N′-ethylenebis(salicylideneiminato) dianion; salcy=N,N′-(1,2-cyclohexanediylethylene)bis(salicylideneiminate) were synthesized and characterized structurally and magnetically. The results reveal that 1 and 2 are discrete 0-D structures while 3 and 4 are 1-D zigzag neutral chains. Notably, the out-of-plane Mn2 dimer, {[MnIII(5-CH3O-salen)(H2O)]22+ and [FeIII(mpzcq)(CN)3]− are both presented in 2 with the Mn2 dimer being further organized into 1-D supramolecular chain arrangement via hydrogen bonds interactions. Magnetic investigation indicates that weak intradimer ferromagnetic coupling exists in 2 while dominant intrachain antiferromagnetic couplings in 3 and 4. Moreover, slow magnetic relaxations were also observed for 2 and 3.

Magnetic properties and molecular structure of a binuclear alternative bridged Cu(II)Re(IV) complex containing a macrocyclic ligand

Two novel macrocyclic compounds, the heterobimetallic complex {(CuLα)[ReCl4(ox)]}n (1) and the mononuclear complex [CuLα]·2ClO4 (2) (where Lα=N-meso-5,12-Me2-7,14-Et2-[14]-4,11-dieneN4), have been synthesized and their crystal structures were determined by the single-crystal X-ray diffraction technique. Complex 1 crystallizes in the monoclinic space group P21/c, whereas 2 crystallizes in the monoclinic space group P21/n. The [CuLα]2+ macrocyclic cation in 1 is coordinated from above and below by [ReCl4(ox)]2− units through the chloro- and monodentate oxalato ligands, and this creates an alternating chloro-oxalato-bridged heterometallic ReIV–CuII one-dimensional zig-zag chain. Their magnetic measurements were carried out over the temperature range 1.8–300K using a Quantum Design SQUID magnetometer (MPMSxL-5 type). Compound 1 behaves like a ferrimagnetic CuII–ReIV dimetallic chain with two intrachain antiferromagnetic coupling parameters and strong single-ion anisotropy, D(Re)=109cm−1. Compound 2 shows weakly interacting paramagnetic centers in the crystal lattice. The effects of hydrogen bonds mediating the magnetic exchange interactions on the spin density have been evidenced by DFT calculations.

First one-dimensional homochiral stairway-like Cu(ii) chains: crystal structures, circular dichroism (CD) spectra, ferroelectricity and antiferromagnetic properties

The reactions of enantiopure chiral ligands (+)/(−)-4,5-pinenepyridyl-2-pyrazine (LS/LR) with CuCl2·2H2O in CH3OH/CH2Cl2 solution led to the formations of one-dimensional homochiral enantiomeric pairs with the formula [Cu(LR/S)Cl2]n·2H2O (R-1 and S-1, the isomers containing the LR and LS ligands, respectively). The circular dichroism (CD) spectra verified their chiroptical activities and enantiomeric natures. Their structures have been determined by X-ray single-crystal analyses, showing stairway-like and mirror-symmetric features, which represent the first examples of homochiral metal complexes with stairway-like structures. The ferroelectric property measurement indicated that R-1 exhibits ferroelectricity with the remnant polarization (Pr) value of 0.02 μC cm−2 under an applied electric field of 6.1 kV cm−1 at room temperature. The magnetic investigation of R-1 showed a weak intrachain antiferromagnetic coupling between Cu(II)–Cu(II) ions mediated by pyrazine, which can be interpreted by a spin-polarization mechanism. All these results suggested that R-1 and S-1 are potential multifunctional molecule-based materials combining optical activity, ferroelectricity and magnetism within one molecule.

Synthesis, structural, thermal, and magnetic investigations of Co(II), Ni(II), and Mn(II) pyrophosphate chains

The reaction in water of cobalt(II), nickel(II) or manganese(II) chloride with 1,10-phenanthroline (phen) and sodium pyrophosphate (Na4P2O7) at low pH (∼2) afforded three isostructural pyrophosphate complexes of an unprecedented one-dimensional typology, namely, {[M(phen)(H2O)(H2P2O7)]·H2O}n with M=Co(1), Ni(2) and Mn(3). The di-hydrogen-pyrophosphate anion featured in these complexes adopts a rare bidentate/monodentate bridging mode leading to chain propagation. This unusual bridging pathway produces a metal–metal intra-chain separation of about 6.6–6.7Å for 1–3, values much larger than the metal–metal distance across the classic bis-bidentate PPi in the parent homodinuclear complexes {[Co(phen)2]2(μ-P2O7)}·6MeOH (1a), {[Ni(phen)2]2(H2O)(μ-P2O7)}·27H2O (2a) and {[Mn(phen)2]2(H2O)(μ-P2O7)}·13H2O (3a), corresponding to ca. 4.9, 5.0 and 4.7Å, respectively. Variable-temperature magnetic susceptibility measurements on polycrystalline samples of 1–3 revealed weak intrachain antiferromagnetic couplings [J=−0.93 (1), −1.88 (2) and −0.26cm−1 (3)], consistent with previous data on the dinuclear complexes 1a–3a.

Constructing Single-Chain Magnets by Supramolecular π-π Stacking and Spin Canting: A Case Study on Manganese(III) Corroles

A single-chain magnet (SCM) was constructed from manganese(III) 5,10,15-tris(pentafluorophenyl)corrole complex [Mn(III) (tpfc)] through supramolecular π-π stacking without bridging ligands. In the crystal structures, [Mn(tpfc)] molecules crystallized from different solvents, such as methanol, ethyl acetate, and ethanol, exhibit different molecular orientations and intermolecular π-π interaction or weak Mn⋅⋅⋅O interaction to form a supramolecular one-dimensional motif or dimer. These three complexes show very different magnetic behaviors at low temperature. Methanol solvate 1 shows obvious frequency dependence of out-of-phase alternating-current magnetic susceptibility below 2 K and a magnetization hysteresis loop with a coercive field of 400 Oe at 0.5 K. It is the first example of spin-canted supramolecular single-chain magnet due to weak π-π stacking interaction. By fitting the susceptibility data χ(M) T (20-300 K) of 1 with the spin Hamiltonian expression H = -2J Σ(i=1)(n-1) S(Ai) S(Ai+1) + D Σ(i) S((iZ)(2)), the intrachain magnetic coupling parameter transmitted by π-π interaction of -0.31 cm(-1) and zero field splitting parameter D of -2.59 cm(-1) are obtained. Ethyl acetate solvate 2 behaves as an antiferromagnetic chain without ordering or slow magnetic relaxation down to 0.5 K. The magnetic susceptibility data χ(M) T (20-300 K) of 2 was fitted by assuming the spin Hamiltonian H = -2JΣ(i=1)(n-1) S(Ai) S(Ai+1), and the intrachain antiferromagnetic coupling constant of -0.07 cm(-1) is much weaker than that of 1. Ethanol solvate 3 with a dimer motif shows field-induced single-molecule magnet like behavior below 2.5 K. The exchange coupling constant J within the dimer propagated by π-π interaction is -0.14 cm(-1) by fitting the susceptibility data χ(M) T (20-300 K) with the spin Hamiltonian H = -2J S(A) S(B) + β(S((A)g(A)) + S((B)g(B)))H. The present studies open a new way to construct SCMs from anisotropic magnetic single-ion units through weak intermolecular interactions in the absence of bridging ligands.

Magnetic properties of the antiferromagnetic spin-12chain systemβ-TeVO4

The magnetic susceptibility and magnetization of high quality single crystal beta-TeVO4 are reported. We show that this compound, made of weakly coupled infinite chains of VO5 pyramids sharing corners, behaves as a S = 1/2 one-dimensional Heisenberg antiferromagnet. From magnetic experiments we deduce the intrachain antiferromagnetic coupling constant J/kB = 21.4 $\pm$ 0.2 K. Below 5 K a series of three phase transitions at 2.26, 3.28 and 4.65 K is observed.

Structural and Electronic Modulation of Magnetic Properties in a Family of Chiral Iron Coordination Polymers

The complexes FeL(2) [L = bidentate Schiff base ligands obtained from (R)-(+)-α-phenylethanamine and 4-substituted salicylaldehydes, substituent R = H, (t)Bu, NO(2), OMe, CN, OH] react with ditopic proligands 1,4-pyrazine (pz) or 4,4'-bipyridine (bpy), to give a family of optically pure Fe(II) polymeric chain complexes of formula {FeL(2)(μ-pz)}(∞) and {FeL(2)(μ-bpy)}(∞). Crystallographic studies show that a range of structures are formed including unidirectional and bidirectional linear polymers and canted zigzag chains. Interchain interactions via π-contacts and hydrogen bonding are also observed. SQuID magnetometry studies on all of the complexes reveal antiferromagnetic interactions, the magnitudes of which are rationalized on the basis of substituent electronic properties and bridging ligand identity. For complexes with bridging pz, the antiferromangnetic interaction is enhanced by electron-releasing substituents on the Fe units, and this is accompanied by a contraction in the intrachain distance. For complexes bridged with the longer bpy the intrachain antiferromagnetic couplings are much weaker as a result of the longer intrachain distance. The magnetic data for this series of chain complexes follow a Bonner-Fisher 1D chain model, alongside a zero field splitting (ZFS) model for Fe(II) (S = 2) as appropriate. The intrachain antiferromagnetic coupling J values, g-factors, and the axial ZFS parameter D were obtained.

Synthesis, Crystal Structures and Magnetic Properties of MIICuII Chains (M=Mn and Co) with Sterically Hindered Alkyl‐Substituted Phenyloxamate Bridging Ligands

A series of neutral oxamato-bridged heterobimetallic chains of general formula [MCu(L(x)2 (S)2] · p S · q H2O [p = 0-1, q = 0-2.5; L1 = N-2,6-dimethylphenyloxamate, S = DMF with M = Mn (1a) and Co (1b); L2 = N-2,6-diethylphenyloxamate, S = DMF with M = Mn (2a) and Co (2b) or S = DMSO with M = Mn (2c) and Co (2 d); L3 = N-2,6-diisopropylphenyloxamate, S = DMF with M = Mn (3a) and Co (3b) or S = DMSO with M = Mn (3c) and Co (3d)] were prepared by treating the corresponding anionic oxamatocopper(II) complexes [Cu(L(x))(2)]2- (x = 1-3) with M(2+) cations (M = Mn and Co) in DMF or DMSO as the solvent. The single-crystal X-ray structures of 2a and 3a reveal the occurrence of well-isolated, zigzag, oxamato-bridged manganese(II)-copper(II) chains. The intrachain Cu···Mn distances across the oxamato bridge are 5.3761(7) and 5.4002(17) Å for 2a and 3a, respectively, whereas the shortest interchain Mn···Mn distances are 9.4475(16) and 8.1649(14) Å for 2a and 3 a, respectively. All of these M(II) Cu(II) chains (M = Mn and Co) exhibit 1D ferrimagnetic behaviour with moderately strong intrachain antiferromagnetic coupling between the square-planar Cu(II) and octahedral high-spin M(II) ions across the oxamato bridge [-J=31.4-35.2 and 33.4-44.8 cm(-1) , respectively; H = ∑(i)-JS(M,i) (S(Cu,i) +S(Cu,i-1))]. Only the Co(II) Cu(II) chains show slow magnetic relaxation effects characteristic of single-chain magnets (SCMs). Analysis of the magnetic relaxation dynamics of 3d shows a thermally activated mechanism (Arrhenius law dependence) with values of the pre-exponential factor (τ(0) = 2.6 × 10(-9) s) and activation energy (E(a) =7.7 cm(-1) ) that are typical of SCMs. In contrast, two relaxation regimes are observed for 2d in different temperature regions (τ(0) = 3.2 × 10(-10) s and E(a) = 24.7 cm(-1) for T < 4.5K and τ(0) = 3.2 × 10(-14) s and E(a) = 37.5 cm(-1) for T>4.5K).

The use of trans-4-cotininecarboxylate to construct a polymeric copper(II) azido complex: Hydro(solvo)thermal synthesis, structure and magnetic properties

A new pyridyl-carboxylate ligand, the anion of trans-4-cotininecarboxylic acid, H L, 1, has been used to prepare a new polymeric copper(II) complex, [Cu LN 3] 2 n , 2, based on a [Cu LN 3] 2 dimeric building block. The single crystal structures of both 1 and 2 have been determined and 1 has been found to be in its zwitterionic configuration. The structure of 2 is a one-dimensional tape-like polymeric structure based on an end-on azido-bridged binuclear [Cu 2N 3] 2 backbone moiety. Magnetic studies reveal that 2 is close to paramagnetic from 2 to 300 K with a Curie constant of 1.094 emu K/mol, a Weiss temperature of 0.73 K and a corresponding μ eff of 2.09 μ B. A fit of χ MT for 2 with S 1 = S 2 = ½, yields g = 2.441(6), J = −0.49(3) cm −1, zJ = −0.38(2) cm −1 and N( α) = 0.00053(12) emu/mol, a fit that indicates the presence of both very weak intramolecular intrachain antiferromagnetic exchange coupling within the one-dimensional tape-like chains and very weak interchain antiferromagnetic exchange coupling between these chains.

Low-Dimensional Structure and Magnetism of the Quantum Antiferromagnet Rb4Cu(MoO4)3 and the Structure of Rb4Zn(MoO4)3

Single crystals of the quantum low-dimensional antiferromagnet Rb(4)Cu(MoO(4))(3) and the nonmagnetic analogue Ru(4)Zn(MoO(4))(3) have been synthesized by a flux-growth method. Detailed structural studies indicate that the Cu(II)-O network separated by a MoO(4) layer has a strongly anisotropic hybridization along the a-axis, forming a quasi-one-dimensional (1-d) chain of Cu(II) S = 1/2 spins. Furthermore, our low-temperature thermodynamic measurements have revealed that a quantum paramagnetic state with Wilson ratio approximately 2 remains stable down to at least 0.1 K, 100 times lower than the intrachain antiferromagnetic coupling scale. The low-temperature magnetic and thermal properties are found to be consistent with theoretical predictions made for a 1-d network of S = 1/2 spins.

ReCl4(CN)2]2−: A High Magnetic Anisotropy Building Unit Giving Rise to the Single-Chain Magnets (DMF)4MReCl4(CN)2 (M = Mn, Fe, Co, Ni)

An S = 3/2, high-anisotropy building unit, trans-[ReCl(4)(CN)(2)](2-), representing the first paramagnetic complex with a mixture of just cyanide and halide ligands, has been synthesized through the reaction of (Bu(4)N)CN with ReCl(4)(THF)(2). This species is characterized in detail and employed in directing the formation of a series of one-dimensional coordination solids of formula (DMF)(4)MReCl(4)(CN)(2) (M = Mn (2), Fe (3), Co (4), Ni (5)). Variable-temperature dc magnetic susceptibility measurements demonstrate the presence of intrachain antiferromagnetic (2) and ferromagnetic (3-5) exchange coupling within these solids. In addition, probing the ac magnetic susceptibility as a function of both temperature and frequency reveals that all of the chain compounds exhibit slow relaxation of the magnetization. The relaxation time is shown to be thermally activated, with energy barriers to relaxation of Delta(tau) = 31, 56, 17, and 20 cm(-1) for 2-5, respectively. Notably, the field-dependent magnetization of the iron congener exhibits a significant hysteresis effect at low temperature, with a coercive field of H(C) = 1.0 T, thus demonstrating magnetlike behavior in this one-dimensional system. Finally, the magnetization dynamics of all solids occur within the finite-size regime, where the magnetic domain growth is limited due to physical defects along the chains within the crystals.