Antiferromagnetic Intrachain Interactions Research Articles

Inducing Ferrimagnetic Exchange in 1D-FeSe2 Chains Using Heteroleptic Amine Complexes: [Fe(en)(tren)][FeSe2]2.

[Fe(en)(tren)][FeSe2]2 (en = ethylenediamine, C2H8N2, tren = tris(2-aminoethyl)amine, C6H18N4) has been synthesized by a mixed-ligand solvothermal method. Its crystal structure contains heteroleptic [Fe(en)(tren)]2+ complexes with distorted octahedral coordination, incorporated between 1D-FeSe2 chains composed of edge-sharing FeSe4 tetrahedra. The twisted octahedral coordination environment of the Fe-amine complex leads to partial dimerization of Fe-Fe distances in the FeSe2 chains so that the FeSe4 polyhedra deviate strongly from the regular tetrahedral geometry. 57Fe Mössbauer spectroscopy reveals oxidation states of +3 for the Fechain atoms and +2 for the Fecomplex atoms. The close proximity of Fe atoms in the chains promotes ferromagnetic nearest neighbor interactions, as indicated by a positive Weiss constant, θ = +53.8(6) K, derived from the Curie-Weiss fitting. Magnetometry and heat capacity reveal two consecutive magnetic transitions below 10 K. DFT calculations suggest that the ordering observed at 4 K is due to antiferromagnetic intrachain interactions in the 1D-FeSe2 chains. The combination of two different ligands creates an asymmetric coordination environment that induces changes in the structure of the Fe-Se fragments. This synthetic strategy opens new ways to explore the effects of ligand field strength on the structure of both Fe-amine complexes and surrounding Fe-Se chains.

Low-Dimensional Magnetism in Multivariate Copper/Zinc MOF-74 Materials Formed via Different Mechanochemical Methods.

MOF-74 is an archetypal magnetic metal-organic framework (MOF) family, with metal nodes bridged by 2,5-dioxido-1,4-benzenedicarboxylic acid (H4dobdc) and arranged into one of the simplest representations of the 1D Ising magnetic model. Recently, a novel mechano-synthetic approach opened a pathway toward a series of bimetallic multivariate (1:1) M1M2-MOF-74 materials, with the uniform distribution of metal cations in the oxometallic chains, offering a unique opportunity to investigate low-dimensional magnetism in these heterometallic MOFs. We explore here how different mechanochemical procedures affect the interaction between the metal nodes of the model system of three multivariate copper(II)/zinc(II)-MOF-74 materials, two of which were obtained through a template-controlled procedure, and the third one was obtained by recently developed mechanical MOF-alloying combined with subsequent accelerated aging. While the three Cu/Zn-MOF-74 products have almost identical powder X-ray diffraction (PXRD) diffractograms and Fourier transform infrared spectra, they differ significantly in their magnetic properties, as revealed through detailed magnetization and X-band and multifrequency high-field electron spin resonance measurements. The magnetic results of the three multivariate Cu/Zn-MOF-74s were compared to the properties of the monometallic Cu-MOF-74, which shows antiferromagnetic intrachain and weaker ferromagnetic interchain interactions. Energy-dispersive X-ray spectroscopy/scanning electron microscopy and solid-state nuclear magnetic resonance spectroscopy helped rationalize the observed differences in magnetization, and in situ synchrotron PXRD monitoring of template-controlled MOF formation revealed different reaction pathways when using the zinc or copper intermediates, involving even the fleeting occurrence of a rare MOF-74 polymorph.

Synthesis, structures and magnetic properties of two new hydrazine bridged 1D cobalt(II) coordination polymers

Two new hydrazine bridged 1D CoII coordination polymers formulated as [Co(N2H4)2F]Cl (1) and Co(N2H4)(H2O)2F2 (2) have been synthesized and magnetically characterized. Compound 1 consists of one-dimensional hydrazine-fluoride mixed bridged CoII chain, while compound 2 exhibits hydrazine bridged CoII chain with fluoride as terminal ligand. Magnetic susceptibility measurements reveal that compound 1 exhibits 1D antiferromagnetic characterization with a long-range ordering at 10.2 K, while compound 2 does not show long-range ordering above 2 K with antiferromagnetic intrachain interactions.

Helimagnetism in MnBi2Se4 Driven by Spin-Frustrating Interactions Between Antiferromagnetic Chains

We report the magnetic properties and magnetic structure determination for a linear-chain antiferromagnet, MnBi2Se4. The crystal structure of this material contains chains of edge-sharing MnSe6 octahedra separated by Bi atoms. The magnetic behavior is dominated by intrachain antiferromagnetic (AFM) interactions, as demonstrated by the negative Weiss constant of −74 K obtained by the Curie–Weiss fit of the paramagnetic susceptibility measured along the easy-axis magnetization direction. The relative shift of adjacent chains by one-half of the chain period causes spin frustration due to interchain AFM coupling, which leads to AFM ordering at TN = 15 K. Neutron diffraction studies reveal that the AFM ordered state exhibits an incommensurate helimagnetic structure with the propagation vector k = (0, 0.356, 0). The Mn moments are arranged perpendicular to the chain propagation direction (the crystallographic b axis), and the turn angle around the helix is 128°. The magnetic properties of MnBi2Se4 are discussed in comparison to other linear-chain antiferromagnets based on ternary mixed-metal halides and chalcogenides.

Coordination polymers containing a pyrazole-based ligand and 4,4′-bipyridine as a spacer: enhancing the family of nonzero-dimensional compounds featuring single-ion magnetic behavior

Two coordination polymers with molecular formula 1∞[M(L)2(4,4′-bipy)(H2O)2], where M stands for CoII (1) or CuII, (2), and L = 5-amino-1-phenyl-1H-pyrazole-4-carboxylate ligand were obtained by slow solvent diffusion and characterized by spectroscopic techniques, single crystal and powder X-ray diffraction, magnetic measurements, and DFT calculations. Magnetic studies carried out for complex 1 showed the key role played by the zero-field splitting and the experimental fit parameters were correlated to CASSCF calculations. Moreover, AC magnetic measurements for 1 revealed a field-induced slow relaxation of the magnetization and a single-ion magnet behavior. For the copper-containing polymer, two kinds of magnetic interactions were observed in the magnetic data and confirmed by using broken-symmetry DFT calculations: (i) ferromagnetic interchain coupling mediated by the hydrogen-bonds and (ii) antiferromagnetic intrachain interaction through the 4,4′-bipy ligand.

Preparation and magnetic properties of o-LiMnO2

Pure o-LiMnO2 prepared by solid state reaction under Ar flow at 850 °C crystallizes in an orthorhombic symmetry (SG: Pmnm). Mn3+ with four unpaired electrons is subjected to a strong Jahn-Teller (J-T) distortion, where the MnO6 octahedron is significantly elongated (1.17%) along the c axis. In air, the oxide converts to spinel LiMn2O4 at ∼320 °C. The magnetic susceptibility of LiMnO2, measured between 4.2 and 900 K, indicates a long range order. The negative θP value (−790 K) reveals strong antiferromagnetic interactions between half-filled dz21 orbital. The predominant interaction is negative and occurs between Mn3+ and its next-nearest neighbors via O2− ions by super exchange with Mn3+-O: 2p-Mn3+ angle of 178°. Above 300 K, the susceptibility follows a Curie Weiss law with a magnetic moment of 5.26 μB consistent with the high spin state Mn3+ (t2g3 eg1) but slightly larger than the spin only contribution for the ground state 5Do. The susceptibility is field dependent down to 4.2 K and a spin canting has been detected at low temperature. As magnetic chains are separated by non-magnetic Li ones, the interactions are confined along the [1 1 0] direction and one can expect a good realization of one dimensional model. Therefore, the magnetic data have been fitted on the base of the isotropic model for finite linear chain in terms of intra-chain antiferromagnetic interactions using the Fisher model. The best fitting is obtained for a value of J/k = −60 K. The results are compared with those of the crednerite CuMnO2 with smaller J/k value (−33 K).

Magnetism in Heterobimetallic and Heterotrimetallic Chains Based on the Use of [WV(bipy)(CN)6]– as a Metalloligand

Two new heterobi‐ and trimetallic chains of formula ∞1[{MnII(pyim)2}{(µ‐NC)2WV(bipy)(CN)4}][WV(bipy)(CN)6] (1) and ∞1[{CuIIMnIIL}{(µ‐NC)3WV(bipy)(CN)3}][WV(bipy)(CN)6]·0.75H2O·2MeCN (2) were obtained by reacting the cyanido‐based AsPh4[W(bipy)(CN)6] heteroleptic complex with the pre‐formed [MnII(pyim)2]2+ (1) and [CuIIMnIIL]2+ (2) complexes [bipy = 2,2′‐bipyridine, pyim = 2‐(1H‐imidazol‐2‐yl)pyridine and H2L = macrocyclic Schiff‐base resulting from the stepwise condensation of 2,6‐diformyl‐p‐cresol with ethylenediamine and diethylenetriamine]. The structure of 1 consists of cationic cyanido‐bridged {MnIIWV} chains, assembled from [WV(bipy)(CN)6]– spacers, each one coordinating in a bis‐monodentate fashion, two [MnII(pyim)2]2+ nodes, and [WV(bipy)(CN)6]– counteranions. Compound 2 comprises a positively charged 1D coordination polymer, built from [WV(bipy)(CN)6]– cyanido metalloligands that act as tris‐monodentate spacers towards [CuIIMnIIL]2+ complexes, the entire assembly being neutralized by [WV(bipy)(CN)6]– anions. Each manganese(II) ion in 1 is six‐coordinate in a somewhat distorted octahedral surrounding. Five‐coordinate copper(II) and seven‐coordinate manganese(II) ions exhibiting distorted square pyramidal and monocapped trigonal prism environments respectively, occur in each {CuIIMnII} node of 2. The magnetic susceptibility of 1 and 2 investigated down to 1.9 K is characteristic of 1D ferrimagnetic behavior with minima in the χMT vs. T plots at 35 (1) and 20 K (2) (χM is the magnetic susceptibility per one MnII plus two WV ions). The magnetic data of 1 in the whole temperature range were analyzed through a model considering SMn = 5/2 as a classical spin and SW = 1/2 as a quantum spin, with two interaction parameters J1 = J(1 – α) and J2 = J(1 + α) {the spin Hamiltonian being defined as H = –JΣiSW,i[(1 + α)SMn,j + (1 – α)SMn,i+1] + Σi(gWSW,i + gMnSMn,i)βH}. The values of the intrachain antiferromagnetic interactions for 1 through this model were –3.0(1) (J1) and –32.0(1) cm–1 (J2). The complexity of the spin topology in 2, a branched chain with four different intrachain antiferromagnetic interactions (double phenoxido bridge between MnII and CuII, two single cyanido bridges between MnII and CuII, and one single cyanido bridge between CuII and WV) precluded any simulation of its magnetic data.

Spin-wave dynamics and exchange interactions in multiferroic NdFe3(BO3)4 explored by inelastic neutron scattering

Magnetic excitations and exchange interactions in multiferroic NdFe3(BO3)4 were studied by inelastic neutron scattering in the phase with commensurate antiferromagnetic structure. The observed spectra were analyzed in the frame of the linear spin-wave theory. It was shown that only the model, which includes the exchange interactions within eight coordination spheres, describes satisfactorily all observed dispersion curves. The calculation showed that the spin-wave dynamics is governed by the strongest antiferromagnetic intra-chain interaction and three almost the same inter-chain interactions. Other interactions, including ferromagnetic exchange, appeared to be insignificant. The overall energy balance of the antiferromagnetic inter-chain exchange interactions, which couple the moments from the adjacent ferromagnetic layers as well as within a layer, stabilizes ferromagnetic arrangement in the latter. It demonstrates that the pathway geometry plays a crucial role in forming of the magnetic structure.

A one-dimensional Mn(II)-based metal organic oxide: structure and properties

A one-dimensional metal organic oxide of Mn(II), with formula [Mn3(OH)2(Hpdc)2]n (H3pdc = 3,5-pyrazoledicarboxylic acid), was prepared via the hydrothermal method and its structure solved by single-crystal X-ray diffraction. The compound exhibits a three-dimensional framework structure, comprising three crystallographically unique Mn atoms bridged by OH ligands (O9 and O10) and O atoms from the Hpdc ligands, forming one-dimensional metal–organic oxide chains. Two kinds of magnetic exchange are observed: a strong antiferromagnetic intra-chain interaction, arising from the short distance between Mn(II) centers, and a ferromagnetic inter-chain interaction, due to the larger distances between the chains. The compound shows good photocatalytic activity for the decomposition of methylene blue in aqueous medium under simulated sunlight.

Crystal structure and characterization of a novel layered copper-lithium phosphonate with antiferromagnetic intrachain Cu(II)···Cu(II) interactions

Novel metal phosphonate [CuLi(PPA)] [H3PPA=3-phosphonopropionic acid] was synthesized hydrothermally and characterized by single-crystal X-ray diffraction, powder X-ray diffraction, scanning electron microscopy, infrared spectroscopy, and thermogravimetric analysis. It crystallizes in the space group C2/c, with cell parameters a=21.617(2) Å, b=4.9269(2) Å, c=14.342(1) Å, β=132.3(2)°, and Z=8. Its framework is built up from a main trimer, acting as a secondary building unit (SBU), which is formed by vertex-shared between two {LiO4} and one {Cu(1)O4} polyhedra. These units repeat along b-axis forming infinite inorganic chains, these chains are in turn cross-linked by corner sharing with {Cu(2)O4} polyhedra to produce inorganic layers lying in the bc-plane. The neighboring layers are connected through the PPA ligand, leading to a 3D pillared-layered structure. The topological analysis reveals that the compound exhibits 3,4,10-c net. Finally, magnetic susceptibility measurement of this compound over the temperature range of 2–300K reveals the occurrence of weak antiferromagnetic intrachain interactions.

Two Cyanide-Bridged Mn(II)-Nb(IV) Coordination Chain Ferrimagnets Promoted by Interchain Ferromagnetic Interactions.

Two new coordination chain compounds based on octacyanoniobate(IV) are reported: {[Mn(II)(bpy)(H2O)2]2[Nb(IV)(CN)8]·5H2O}n (1) and {[Mn(II)(bpy)(H2O)2][Mn(II)(bpy)2][Nb(IV)(CN)8]·5H2O}n (2) (bpy = 2,2'-bipyridine). Both have the topology of vertex-sharing CN-bridged squares. The Mn2Nb2 units are mutually parallel in 1 and perpendicular in 2. The antiferromagnetic intrachain interactions between the Mn(II) and Nb(IV) centers in 1 and 2, typical for Mn(II)-[Nb(IV)(CN)8] family of compounds, lead to ferrimagnetic ground state of each single chain. Both compounds show bulk ferrimagnetic ordering below their critical temperatures (Tc) of 6.4 K in 1 and 4.7 K in 2. Such a behavior is due to the ferromagnetic interchain interactions, assured by the π-π contacts between the 2,2'-bipyridine rings and by the hydrogen bonds between the terminal cyanide ligands of the [Nb(IV)(CN)8]-building blocks and coordination/crystallization water molecules. 1 and 2 are rare examples of ferrimagnets promoted by interchain ferromagnetic exchange, and the Tc of 1 is one of the highest among similar 1-D coordination polymers.

Two S = 1/2 one-dimensional barium copper phosphates showing antiferromagnetic and ferromagnetic intrachain interactions.

Two barium copper phosphates, BaCu2(PO4)2(H2O) (1) and Ba2Cu(HPO4)(PO4)(OH) (2), were synthesized under mild hydrothermal conditions. The Cu cation in 1 adopts a CuO4(H2O) square pyramidal coordination configuration, forming alternating chains along the b axis through alternative corner and edge sharing, while the geometry of the Cu center in 2 is a CuO4(OH)2 octahedron which further connects each other by edge sharing to constitute uniform chains along the b axis. Magnetic behaviors of both compounds were analyzed by susceptibility, magnetization and heat capacity measurements. The dominant intrachain couplings are antiferromagnetic in 1 with a long-range ordering at 14 K and ferromagnetic in 2 without long-range ordering above 2 K. The first principles calculations indicate that the intrachain ferromagnetic couplings in 2 originate from Cu(1)-O(7)H-Cu(1) dpσ correlation superexchanges. The susceptibility data of compounds 1 and 2 are fitted by using suitable antiferromagnetic chain and ferromagnetic chain models, respectively. In addition, we report the results of the infrared and thermal measurements of both the compounds.

Crystal Structures and Magnetic Properties of Nickel Chain Compounds PbM2Ni6Te3O18 (M = Mn, Cd)

The synthesis, crystal structures, and magnetic properties of the pentanary oxides PbM2Ni6Te3O18 (M = Mn and Cd) were investigated. These compounds crystallize in a hexagonal structure with space group P63/m, in which the Ni(2+) ions form a zigzag chain along the c axis. From the magnetic susceptibility and specific heat measurements, we found that the PbCd2Ni6Te3O18 behaves as a low-dimensional magnet due to the intrachain antiferromagnetic interaction between Ni(2+) ions. Both compounds show a long-range antiferromagnetic ordering at 25.7 K (M = Cd) and 86.0 K (Mn). The magnetic structure of PbMn2Ni6Te3O18 determined by neutron diffraction measurements is a collinear antiferromagnetic arrangement of Mn(2+) ions in the Mn2O9 dimeric unit and Ni(2+) ions in the zigzag chain.

Spin dynamics of Mn pyrochlore lattice in YMn2Zn20-xInx

It is shown in a new class of pyrochlore compound YMn2Zn20-xInx (with x = 2.36) that the spin fluctuation rate (v) is proportional to temperature (v ∝ T) below T0 ~10 K where heavy-fermion(HF)-like behavior is observed. Such a linear T dependence, commonly found in Y(Sc)Mn2 and LiV2O4, is expected for intersecting quasi-1D Hubbard chains, suggesting that the quasi-1D character of the t2g band associated with the pyrochlore lattice plays an important role in the emergence of the HF-like state, where T0 may correspond to intra-chain antiferromagnetic interaction energy between Mn spins.

Unusual magnetic behaviors and electronic configurations driven by diverse Co(II) or Mn(II) MOF architectures.

Five novel metal organic frameworks were obtained by hydro-solvothermal reactions using the hexafluorisopropylidenebis(benzoic) acid (H2hfipbb) as linker and Co(II) or Mn(II) ions as connectors. [Co2(Hhfipbb)(TEA)], compound 1 (TEA = triethanolamine trianion) with a three-dimensional (3D) framework, and a tpu net; [Co1.5(hfipbb)2]·HN(CH2CH3)3 and [Co3(hfipbb)2]·2{HN(CH2CH3)3}, compounds 2 and 2-a, respectively, both with two-dimensional structure, sql topologies, and different layer packings. Compounds 3 and 4, having the general formula [M2(hfipbb)2]·C7H8, where M = Co (3) or Mn (4), have 3D frameworks with an sqc topology. A deep analysis of the magnetic measurements reveals different striking magnetic behaviors resulting from diverse secondary building unit and framework architectures. Compound 1 presents canted antiferromagnetic chains, compound 2 contains ferromagnetic linear trimeric clusters, and compound 3 exhibits ferromagnetic chains. For the three compounds, a 3D canted antiferromagnetic structure takes place at ∼8 K by means of weak magnetic interactions between the mentioned magnetic units. Such long-range magnetic order is precluded with the application of a high enough magnetic field. Compound 4 evidenced intrachain antiferromagnetic interactions.

Unexpected Strong Antiferromagnetic Interaction in [CuCyclam][Ni(1,2‐benzenedithiolate)2]2

AbstractTwo new molecule‐based magnetic materials were prepared, namely, [CuCyclam(CH3CN)2][Ni(bdt)2]2 and [CuCyclam][Ni(bdt)2]2 (bdt = 1,2‐benzenedithiolate). The former compound is characterized by a two‐dimensional layer structure, in which axially coordinated acetonitrile molecules prevent cation–anion stacking. The weak antiferromagnetic interaction of 2J/kB = –6.2 K between the adjacent [CuCyclam(CH3CN)2]+ (S = 1/2) and [Ni(bdt)2]– (S = 1/2) moieties leads to a ferrimagnetic transition at 2.6 K. In contrast to the structure of [CuCyclam(CH3CN)2][Ni(bdt)2]2, the crystal structure of [CuCyclam][Ni(bdt)2]2 is characterized by alternately stacked [CuCyclam]2+ and [Ni(bdt)2]– units, and another [Ni(bdt)2]– anion bridges the chain to form a two‐dimensional ferrimagnetic layer. The magnetic susceptibility of [CuCyclam][Ni(bdt)2]2 reveals a quite strong intrachain antiferromagnetic interaction of 2J/kB = –66 K between the [CuCyclam]2+ and [Ni(bdt)2]– ions. The weak interchain and interlayer interactions make the crystals antiferromagnetic below 3.2 K.

Influence of Copper(II) and Nickel(II) Ions in the Topology of Systems Based on a Flexible Bis-Oxamate and Bipyridine Building Blocks

Single crystals of the mononuclear bis-oxamate nickel(II) complex [Ni(bipy)(H2edpba)]·dmso (1) are obtained by reacting [Ni(bipy)Cl2]·H2O and the flexible K2(H2edpba) ligand [bipy = 2,2′-bipyridine; H4edpba = N,N′-2,2′-ethylenediphenylenebis(oxamic acid)]. The reaction of 1 with copper(II) ions resulted in two products in which the replacement of the nickel(II) ion by copper(II) took place: the chain compound [Cu(bipy)(H2edpba)]n·3nH2O·ndmso [dmso = dimethyl sulfoxide] (2) and the analogous chain compound without dmso crystallization molecules [Cu(bipy)(H2edpba)]n·1.5nH2O (3a) in its polycrystalline form. The reaction of [Cu(bipy)Cl2] and K2(H2edpba) yielded single crystals of [Cu(bipy)(H2edpba)]n·1.5nH2O (3b). The H2edpba2– ligand exhibits the anti conformation in 1, 2, and 3b, but it adopts different coordination modes: terminal bis-bidentate (1) and bridging bis-bidentate (2 and 3b) through the two pairs of carbonyl-oxygen atoms of the two oxamate arms. Magnetic susceptibility measurements carried out on a polycrystalline sample of 3b in the temperature range 1.9–295 K showed the occurrence of very weak intrachain antiferromagnetic interactions [J = −0.40 cm–1, the Hamiltonian being defined as H = −J ∑iSi·Si+1], in agreement with the large values of the copper–copper separation [8.308(3) Å].

Ligand effects on the structure and magnetic properties of alternating copper(II) chains with 2,2'-bipyrimidine- and polymethyl-substituted pyrazolates as bridging ligands.

A novel series of heteroleptic copper(II) compounds of formulas {[Cu2(μ-H2O)(μ-pz)2(μ-bpm)(ClO4)(H2O)]ClO4·2H2O}n (1), {[Cu2(μ-H2O)(μ-3-Mepz)2(μ-bpm)](ClO4)2·2H2O}n (2), and {[Cu2(μ-OH)(μ-3,5-Me2pz)(μ-bpm)(H-3,5-Me2pz)2](ClO4)2}n (3) [bpm = 2,2'-bipyrimidine, Hpz = pyrazole, H-3-Mepz = 3-methylpyrazole, and H-3,5-Me2pz = 3,5-dimethylpyrazole] have been synthesized and structurally characterized by X-ray diffraction methods. The crystal structures of 1 and 2 consist of copper(II) chains with regular alternating bpm and bis(pyrazolate)(aqua) bridges, whereas that of 3 is made up of copper(II) chains with regular alternating bpm and (pyrazolate)(hydroxo) bridges. The copper centers are six- (1) or five-coordinate (2) in axially elongated, octahedral (1) or square-pyramidal (2) environments in 1 and 2, whereas they are five-coordinate in distorted trigonal-bipyramidal surroundings in 3. The values of the copper-copper separations across the bpm/pyrazolate bridges are 5.5442(7)/3.3131(6) (1), 5.538(1)/3.235(1) (2), and 5.7673(7)/3.3220(6) Å (3). The magnetic properties of 1-3 have been investigated in the temperature range of 25-300 K. The analysis of their magnetic susceptibility data through the isotropic Hamiltonian for an alternating antiferromagnetic copper(II) chain model [H = -J∑i=1-n/2 (S2i·S2i-1 + αS2i·S2i+1), with α = J'/J and Si = SCu = 1/2] reveals the presence of a strong to moderate antiferromagnetic coupling through the bis(pyrazolate)(aqua) [-J = 217 (1) and 215 cm(-1) (2)] and (pyrazolate)(hydroxo) bridges [-J = 153 cm(-1) (3)], respectively, whereas a strong to weak antiferromagnetic coupling occurs through the bis-bidentate bpm [-J' = 211 (1), 213 (2), and 44 cm(-1) (3)]. A simple orbital analysis of the magnetic exchange interaction within the bpm- and pyrazolate-bridged dicopper(II) fragments of 1-3 visualizes the σ-type pathways involving the (dx(2)-y(2)) (1 and 2) or d(z(2)) (3) magnetic orbitals on each metal ion, which account for the variation of the magnetic properties in these three novel examples of one-dimensional copper(II) compounds with regular alternating intrachain antiferromagnetic interactions.

Geometrical Spin Frustration and Ferromagnetic Ordering in (MnxPb2–x)Pb2Sb4Se10

Engineering the atomic structure of an inorganic semiconductor to create isolated one-dimensional (1D) magnetic subunits that are embedded within the semiconducting crystal lattice can enable chemical and electronic manipulation of magnetic ordering within the magnetic domains, paving the way for (1) the investigation of new physical phenomena such as the interactions between electron transport and localized magnetic moments at the atomic scale and (2) the design and fabrication of geometrically frustrated magnetic materials featuring cooperative long-range ordering with large magnetic moments. We report the design, synthesis, crystal structure and magnetic behavior of (MnxPb2-x)Pb2Sb4Se10, a family of three-dimensional manganese-bearing main-group metal selenides featuring quasi-isolated [(MnxPb2-x)3Se30]∞ hexanuclear magnetic ladders coherently embedded and uniformly distributed within a purely inorganic semiconducting framework, [Pb2Sb4Se10]. Careful structural analysis of the magnetic subunit, [(MnxPb2-x)3Se30]∞ and the temperature dependent magnetic susceptibility of (MnxPb2-x)Pb2Sb4Se10, indicate that the compounds are geometrically frustrated 1D ferromagnets. Interestingly, the degree of geometrical spin frustration (f) within the magnetic ladders and the strength of the intrachain antiferromagnetic (AFM) interactions strongly depend on the concentration (x value) and the distribution of the Mn atom within the magnetic substructure. The combination of strong intrachain AFM interactions and geometrical spin frustration in the [(MnxPb2-x)3Se30]∞ ladders results in a cooperative ferromagnetic order with exceptionally high magnetic moment at around 125 K. Magnetotransport study of the Mn2Pb2Sb4Se10 composition over the temperature range from 100 to 200 K revealed negative magnetoresistance (NMR) values and also suggested a strong contribution of magnetic polarons to the observed large effective magnetic moments.

Solvent-driven dimensionality control in molecular systems containing CuII, 2,2′-bipyridine and an oxamato-based ligand

A discrete dicopper(II) system, [Cu(bipy)(H2mpba)]2·2H2O (1), and its isomeric chain, [Cu(bipy)(H2mpba)]·dmso (2) [bipy = 2,2′-bipyridine and H4mpba = N,N′-1,3-phenylenebis(oxamic acid)], were obtained by modifying the ratio of the H2O–dmso solvent mixture, and their interconversion was also monitored by changing the solvents during the synthesis. The solvents play an essential role in the formation and crystallization of these complexes, presenting different dimensionalities and connectivities. The double deprotonated H2mpba2− adopts the bidentate/monodentate (1) and bis-bidentate (2) bridging modes toward the (2,2′-bipyridyl)copper(II) units affording a dinuclear compound (1) and a linear chain (2), respectively. Variable-temperature magnetic measurements show the occurrence of weak intradinuclear (1) and intrachain (2) antiferromagnetic interactions.