Intrachain Ferromagnetic Coupling Research Articles

Ferromagnetically coupled single-chain magnets exhibiting a magnetic hysteresis of 0.42 Tesla in cyano-bridged FeIII2MII (M = Ni, Fe) coordination polymers.

The synthesis, single-crystal structures and magnetic properties of two new double-zigzag-chain cyano-bridged heterobimetallic {[MII(Py-NOH)2][FeIII(Tp*)(CN)3]2}·H2O ([FeIII2MII]) (Py-NOH = 4-pyridinealdoxime, Tp* = tris(3,5-dimethylpyrazol-1-yl)borohydride, M = Ni (1), Fe (2)) compounds are reported. The crystal structures of both compounds were determined by single-crystal X-ray diffraction. Complexes 1 and 2 are isostructural, with the crystal structure comprising neutral double-zigzag (4,2-ribbon-like) bimetallic chains. The FeIII ion is coordinated by three cyanide carbon atoms and three nitrogen atoms of Tp* anions. However, the MII ion is surrounded by four cyanide nitrogen atoms and two nitrogen atoms from two Py-NOH ligands. The crystal structures and magnetic studies demonstrate that both complexes behave as single-chain magnetics (SCMs) with intrachain ferromagnetic coupling. Furthermore, [FeIII2NiII] exhibits an excellent coercive field of 0.42 T at 1.8 K, among cyano-bridged 3d transition-metal-based SCMs reported thus far. Preliminary theoretical calculations provide a deep understanding of the magnetic properties of [FeIII2NiII].

Random Co(II)-Ni(II) Ferromagnetic Chains Showing Coexistent Antiferromagnetism, Metamagnetism, and Single-Chain Magnetism.

A series of isomorphous compounds of general formula [Co1- xNi x(tzpo)(N3)(H2O)2] n· nH2O ( x = 0, 0.19, 0.38, 0.53, 0.68, 0.84, and 1; tzpo = 4-(5-tetrazolate)pyridine- N-oxide) was prepared. The compounds consist of homometallic or heterometallic chains with simultaneous azide-tetrazolate bridges. The heterometallic systems feature random distribution of metal ions. All compounds across the series exhibit intrachain ferromagnetic coupling, interchain antiferromagnetic (AF) ordering, field-induced metamagnetic transition, and, except the Ni-only compound, single-chain magnetic dynamics. The AF ordering temperature, the metamagnetic critical field, and the relaxation parameters show different composition dependence. Notably, the blocking temperature for the Co-rich materials is higher than the Co-only compound, suggesting synergy between the randomly distributed Co(II) and Ni(II) ions in promoting slow relaxation. The results imply rich physics in the random mixed-metal systems and demonstrate the possibility of improving single-chain relaxation properties by blending metal ions.

Developing a magnetic metal organic framework of copper bearing a mixed azido/butane-1,4-dicarboxylate bridge: magnetic and gas adsorption properties.

A magnetic metal organic framework {[Cu(but-1,4-dc)0.5(N3)(H2O)]·H2O}n (MFUM-1(Cu)) (but-1,4-dc = butane-1,4-dicarboxylate) was synthesized and characterized structurally and magnetically. In MFUM-1(Cu), each CuII ion has a distorted octahedral geometry with an obvious Jahn-Teller distortion, where the coordination environment is composed of mixed EO-azido/aliphatic based carboxylate/H2O threefold bridges. These bridges extend the structure of MFUM-1(Cu) in two dimensions by covalent connectivity and form square-shaped channels. Also, a study was done to determine the effectiveness of sonochemical synthesis for the preparation of nano-sheets of MFUM-1(Cu) and subsequently the influence of particle size on physical properties such as magnetic behavior and thermal stability. The particles were characterized by elemental analyses, infrared spectroscopy (IR), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), and powder X-ray diffraction (PXRD) analyses. The effects of parameters such as concentration, solvent, and reaction time on the size distribution, morphology, and yield of product were carefully studied. The magnetic properties of MFUM-1(Cu) and corresponding nano-structure were examined which indicated metamagnetism with strong intrachain ferromagnetic coupling versus the weak interchain antiferromagnetic coupling. Finally, the application of MFUM-1(Cu) in the separation of carbon dioxide from nitrogen and also from methane was theoretically investigated. High calculated selectivity of CO2 over N2 and CH4 reveals the potential application of MFUM-1(Cu) in practical systems of gas separation.

A Series of Chiral, Polar, Homospin Topological Ferrimagnets: M3(OOCH)5Cl(OH2) (M = Fe, Co, Ni)

An isostructural series of transition metal-formate-chloride-hydrate compounds, M3(OOCH)5Cl(OH2) (M = Fe, Co, Ni), have been synthesized using a solvothermal method. These compounds crystallize in the chiral and polar space group P31 and are comprised of three different types of helical chains of edge-sharing M2+-centered octahedra. All three compounds undergo 3D ferrimagnetic ordering at low temperature, and the iron and cobalt analogues exhibit field-induced metamagnetic transitions. The magnetic structure was determined by neutron powder diffraction, revealing ferromagnetic intrachain coupling and antiferromagnetic interchain interactions, with the three chains arranged in a two-up/one-down triangular lattice. As all three chains contain one type of metal in the same spin state, these compounds are rare examples of homospin topological ferrimagnets.

A Rare Water and Hydroxyl-Extended One-Dimensional Dysprosium(III) Chain and Its Magnetic Dilution Effect.

A novel water and hydroxyl-extended one-dimensional dysprosium(III) chain was hydrothermally obtained, which exhibits a relatively high spin-reversal energy barrier of 88.7 K and intrachain ferromagnetic interaction with the coupling constant Jexch = 3.04 cm-1 calculated by fitting magnetic susceptibilities using POLY_ANISO program based on ab initio calculations. To deeply understand the respective role of the single-ion anisotropy and intrachain exchange on the effective energy barrier, three crystallographically isostructural analogues containing isotropic Gd(III)-, diamagnetic Y(III)-, as well as Y(III)-doped Dy0.05Y0.95 were prepared and characterized structurally and magnetically. Due to the absence of significant intrachain exchange interaction, the effective energy barrier of the Dy0.05Y0.95 decreased by 9.9 K as compared with that of parent dysprosium(III) chain. Thus, it can be concluded that the intrachain ferromagnetic coupling and the magnetic anisotropy of the Dy(III) ion synergistically enhance the effective energy barrier of the dysprosium(III) chain, in which the single-ion anisotropy becomes more predominant.

Slow Magnetic Relaxation in One-Dimensional Azido-Bridged CoII Complexes.

Crystal structures and magnetic properties of three one-dimensional (1D) azido-bridged cobalt(II) chains with different amide ligands (L), [Co2(N3)4(DMF)3] (1), [Co4(N3)8(DEF)5] (2), and [Co2(N3)4(DIPF)2] (3) (DMF = N,N-dimethylformamide, DEF = N,N-diethylformamide, and DIPF = N,N-diisopropylformamide), are reported to investigate the influence of L on their structures and magnetic properties. Single-crystal X-ray crystallographic analysis revealed that, although 1-3 all consist of cobalt chains bridged by end-on (EO) azides, the coordination geometry of the CoII ions and the repeating units of the 1D structures are quite different. As the size of L increases, the ratio of L to CoII decreases from 6:4 in 1 to 5:4 and 4:4 in 2 and 3, respectively. In 1, two [CoN5O1] and two [CoN4O2] distorted octahedra form the {[CoN5O1][CoN4O2]2[CoN5O1]} tetramers (denoted as Co4A), which are linked to each other by sharing the N-N edge to form the chain. Similarly, the chain structure of 3 is constructed from a similar tetramer unit {[CoN5][CoN4O2]2[CoN5]} (denoted as Co4B), where half of the CoII centers are in the [CoN5] trigonal bipyramid because of the larger steric effect of the DIPF ligand, while, for compound 2 of the medium-sized amide, it has the transition structure between those of 1 and 3. The chain is composed of two different repeating units: Co4A unit similar to that in 1 and Co4B unit similar to that in 3. Because of their similar structures, compounds 1-3 exhibit analogical magnetic properties. Direct-current magnetic measurements demonstrated that all compounds show intrachain ferromagnetic coupling through the EO azides and interchain anti-ferromagnetic interactions. Alternating-current data revealed the slow magnetic relaxation in the anti-ferromagnetic ordered phases. While compound 1 exhibits spin glass behavior, compounds 2 and 3 behave as the single-chain magnets. This difference might come from the interference of the anti-ferromagnetic ordering on the magnetic dynamic of the magnetic chain.

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.

Synthesis, structures and single chain magnet behavior of a cyano-bridged {Fe2Cu} chain

The reaction of tricyanometallate precursor, (Bu4N)[(pzTp)Fe(CN)3] (pzTp = tetrakis(pyrazolyl)borate) with Cu(ClO4)2·6H2O in the presence of the monodentate 4-styrylpyridine ligand afford one novel one-dimensional (1D) heterobimetallic cyano-bridged chain, [Fe(pzTp)(CN)3]2Cu(4-styrylpyridine)2•2H2O•4CH3OH (1). The molecular structure was determined by single-crystal X-ray diffraction. In compound 1, the FeIII ion is coordinated by three cyanide carbon atoms and three nitrogen atoms of pzTp anions. Whereas, the CuII ion is surrounded by four cyanide nitrogen atoms and two nitrogen atoms from two monodentate 4-styrylpyridine ligands. Magnetic measurements indicate that compound 1 exhibits intrachain ferromagnetic coupling and single-chain magnets behavior.

Synthesis, structure, and magnetic properties of a cyanidebridged Fe(III)-Cu(II) bimetallic double-zigzag chain with slow relaxation of the magnetization

Using Bu4N[Fe(Tp*)(CN)3]− (Tp* = hydrotris(3,5-dimethylpyrazol-1-yl)borate) as the building block to react with CuII and N-methylimidazole, we obtained a one-dimensional (1D) heterobimetallic cyano-bridged chain, [Fe(Tp*)(CN)3]2Cu(N-methylimidazole)2·2H2O (1). The crystal structures and magnetic studies demonstrate that complex 1 exhibits slow relaxation of the magnetization due to strong intrachain ferromagnetic coupling and weak interchain interactions.

Slow Relaxation of the Magnetization in a 4,2-Wavelike FeIII2CoII Heterobimetallic Chain

The reaction of the low-spin iron(III) complex [Fe(dmbpy)(CN)(4)](-) (1) with fully solvated cobalt(II) ions affords the cyanide-bridged heterobimetallic chain {[Fe(III)(dmbpy)(CN)(4)](2)Co(II)(H(2)O)(2)}(n) · 4nH(2)O (2), which exhibits intrachain ferromagnetic coupling and double slow relaxation of the magnetization.

FeIII(dmbpy)(CN)4]−: a new building block for designing single-chain magnets

We herein present the synthesis and magneto-structural study of a new family of heterobimetallic chains of general formula {[Fe(III)(dmbpy)(CN)(4)](2)M(II)(H(2)O)(2)}(n)·pnH(2)O [dmbpy = 4,4'-dimethyl-2,2'-bipyridine; M = Mn (2), Cu (3), Ni (4) and Co (5) with p = 4 (2), 3 (3), 9 (4) and 3.5 (5)] which were prepared by using the mononuclear PPh(4)[Fe(III)(dmbpy)(CN)(4)]·3H(2)O (1) building block (PPh(4)(+) = tetraphenylphosphonium) as a ligand toward fully solvated M(II) ions. The structure of 1 consists of discrete [Fe(III)(dmbpy)(CN)(4)](-) anions, tetraphenylphosphonium cations and noncoordinated water molecules. Complexes 2-5 are isostructural compounds whose structure consists of neutral 4,2-wave like heterobimetallic chains of formula {[Fe(III)(dmbpy)(CN)(4)](2)M(II)(H(2)O)(2)}(n) where the [Fe(III)(dmbpy)(CN)(4)](-) entity adopts a bis-monodentate coordination mode toward trans-[M(II)(H(2)O)(2)] units through two of its four cyanide groups in cis positions. 1 exhibits the magnetic behaviour of magnetically isolated six-coordinate low-spin Fe(III) complexes with an important orbital contribution. 2 behaves as ferrimagnetic Fe(III)(2)Mn(II) chains, whereas 3-5 exhibit intrachain ferromagnetic couplings between the low-spin Fe(III) and either Cu(II) (3), Ni (4) or Co(II) (5) as well as frequency-dependence of the out-of-phase ac susceptibility signals below 3.0 (3), 5.5 (4) and 5.0 K (5). The relaxation time and the energy to reverse the magnetization of 3-5 are related to the anisotropy of the M(II) center and to the intra- and interchain magnetic interactions. Unprecedentedly in the world of cyanide-bearing complexes, 5 exhibits a double slow relaxation of the magnetization.

Chelating Schiff base assisted azide-bridged Mn(ii), Ni(ii) and Cu(ii) magnetic coordination polymers

Four new Mn(II), Ni(II) and Cu(II) coordination polymers [Mn2(L1)(μ(1,1)-N3)2(μ(1,3)-N3)2]n (1), [Ni(L2)2(μ(1,3)-N3)]n(ClO4)n (2), [Cu(L3)(μ(1,1)-N3)(N3)]n (3) and [Cu(L4)(μ(1,1)-N3)2]n (4) (L1 = N,N′-bis(2-pyridylmethylene)ethane-1,2-diamine, L2 = N-(2-pyridylmethylene)methylamine, L3 = N-(2-pyridylmethylene)-3-pyridylamine, L4 = N-(2-pyridylmethylene)-tbutylamine) have been synthesized and characterized by single-crystal X-ray analysis and magnetic measurements. Complex 1 indicates a stoichiometry-dependent structural change (based on Mn:L1:N3 = 2:1:4 molar ratio) and consists of two-dimensional (2-D) (4,4) net layers, in which Mn(II) centers are co-bridged by single end-to-end (EE), double end-on (EO) azide and chelate-bridging L1 ligands. Complex 2 shows a single EE azide-bridged one-dimensional (1-D) Ni(II) chain. Complexes 3 and 4 indicate single EO and double EO azide-bridged 1-D Cu(II) chains, respectively. Complex 1 exhibits weak ferromagnetism due to its intra-layer spin-canting with T(c) = 20 K. Complex 2 shows an unusual intra-chain ferromagnetic coupling and spin-canting behaviour. Both complexes 3 and 4 exhibit intra-chain antiferromagnetic interactions. Magneto-structural parameters for these related complexes were also discussed.

Slow magnetic relaxation in a 4,2-ribbon like FeIII2CoII heterobimetallic chain

The reaction of Co(NO(3))(2)·6H(2)O and 3-benzoylpyridine with the low-spin iron(III) complex, H[Fe(III)(phen)(CN)(4)], in methanol gives rise to a cyanide-bridged heterobimetallic chain [{Fe(III)(phen)(CN)(4)}(2)Co(II)(3-bpe)(2)] (1) that exhibits intrachain ferromagnetic coupling and slow double magnetic relaxation.

Single-chain magnet features in 1D [MnR4TPP][TCNE] compounds

Molecular chains of antiferrimagnetically coupled MnIII-ion (S = 2) and TCNE (tetracyanoethylene) radical moments (s = ½) show different behaviour depending on group R substituted to TPP (tetraphenylporphyrin) and on the substitution site. The compound with R = F in Ortho position is a Single-Chain Magnet (SCM) with blocking temperature Tb = 6.6K, while that with R = F in Meta position shows both blocking (Tb = 5.4 K) and magnetic ordering transition (Tc = 10 K). For bulky groups R = OCnH2n+1, the magnetically ordered phase is observed (Tc ≈ 22 K), which does not however prevent slow relaxation at T <8 K. Magnetic hysteresis with coercive field Hc of 2 T at 2.3 K is like that of SCM. The frequency dependent AC susceptibility in the superimposed DC field reveals common features of all systems. The energy of intrachain ferromagnetic coupling between effective spin units 3/2, relevant at low temperatures, is determined for all compounds and the interchain dipolar coupling is estimated. It is concluded that slow relaxation is inherent for all quasi one-dimensional compounds and for the magnetically ordered ones shows up in the high enough magnetic field.

Slow relaxation of the magnetization in Oximato-bridged heterobimetallic Copper(II)-Manganese(III) chains

The use of the oximato-containing copper(II) complexes, [Cu(Hdeg)2] (H2deg = diethylglyoxime), [Cu(Hmeg)2] (H2meg = methylethylglyoxime) and [Cu(Hdmg)2] (H2dmg = dimethylglyoxime), as ligands toward manganese(II) acetate in methanol afforded the heterobimetallic compounds of formula [MnCu(deg)2(CH3COO)(H2O)2] (1), [MnCu(meg)2(CH3COO)(H2O)2] (2) and [MnCu(dmg)2(CH3COO)(H2O)2] (3) where the starting manganese(II) ion was oxidized to manganese(III) by air. In the lack of single crystals suitable for X-ray diffraction analysis, X-ray absorption techniques (EXAFS and XANES) at 40 K were used for the structural characterization of 1-3. The analysis of the X-ray absorption data reveals that 1-3 are oximato-bridged CuII-MnIII bimetallic chains with elongated octahedral CuN4O2 and MnO6 surroundings. The study of the magnetic properties of 1-3 reveals a metamagnetic-like behavior due to the coexistence of strong intrachain ferromagnetic couplings [J = +52.5 (1), +49.1 (2) and +52.1 cm-1 (3)] and weak interchain antiferromagnetic interactions [j = -0.070 (1), -0.075 (2) and -0.078 cm-1 (3)]. The strict orthogonality between the magnetic orbital of the copper(II) ion and those of the manganese(III) center, together with the well known ability of the oximato group to mediate magnetic interactions when acting as a bridge between two metal ions, account for the relatively strong intrachain ferromagnetic coupling in 1-3. Alternating current susceptibility measurements for 1-3 in the low temperature range under zero dc magnetic field reveal a frequency-dependence of the out-of-phase ac signal as expected for single chain magnets

Electronic structures of quasi-one-dimensional ferrimagnetic insulator Ca 3Co 2O 6

The electronic structures of quasi-one-dimensional ferrimagnetic Ca 3Co 2O 6 are investigated using the generalized gradient approximation (GGA) as well as the GGA plus on-site Coulomb interaction ( GGA + U ) scheme. GGA + U calculations reveal that the interchain ferrimagnetic Ca 3Co 2O 6 is a Mott–Hubbard insulator rather than a metal given from GGA. In addition, we found an on-site U induced 3 z 2 − r 2 orbital ordering on Co pri sublattice which drives the intrachain ferromagnetic coupling along c-axis. Our findings suggest that strong electron-electron correlation plays an important role in Ca 3Co 2O 6.

Three-Dimensional Porous Metal−Organic Frameworks Exhibiting Metamagnetic Behaviors: Synthesis, Structure, Adsorption, and Magnetic Properties

Two isomorphous 3D porous metamagnets, {[M(6)(N(3))(12)L(6)].(H(2)O)(13)}(infinity) (M = Ni(II), 1; Co(II), 2), have been constructed from 2-(1,3,4-thiadiazol-2-ylthio)acetic acid (HL), with azido as the auxiliary ligand. Single-crystal X-ray analysis indicates that the complexes possess hexagonal channels with dimensions of about 8.3 A x 8.3 A along the c axis and void space of about 25% per cell volume. Hydrogen adsorption measurements at 740 Torr and 77 K reveal that hydrogen uptakes of 0.68 and 0.83 wt % were observed in 1 and 2, respectively, with BET surface areas of 309 and 328 m(2)/g. Magnetic measurement reveals that both of them exhibit global metamagnetic behaviors resulted from strong intrachain ferromagnetic couplings and weak interchain antiferromagnetic interactions, with critical fields of 22 kOe and 6 kOe for 1 and 2, respectively.

One‐Dimensional Ferromagnetically Coupled Bimetallic Chains Constructed with trans‐[Ru(acac)2(CN)2]−: Syntheses, Structures, Magnetic Properties, and Density Functional Theoretical Study

Four cyano-bridged 1D bimetallic polymers have been prepared by using the paramagnetic building block trans-[Ru(acac)(2)(CN)(2)](-) (Hacac=acetylacetone): {[{Ni(tren)}{Ru(acac)(2)(CN)(2)}][ClO(4)].CH(3)OH}(n) (1) (tren=tris(2-aminoethyl)amine), {[{Ni(cyclen)}{Ru(acac)(2)(CN)(2)}][ClO(4)].CH(3)OH}(n) (2) (cyclen=1,4,7,10-tetraazacyclododecane), {[{Fe(salen)}{Ru(acac)(2)(CN)(2)}]}(n) (3) (salen(2-)=N,N'-bis(salicylidene)-o-ethyldiamine dianion) and [{Mn(5,5'-Me(2)salen)}(2){Ru(acac)(2)(CN)(2)}][Ru(acac)(2)(CN)(2)].2CH(3)OH (4) (5,5'-Me(2)salen=N,N'-bis(5,5'-dimethylsalicylidene)-o-ethylenediimine). Compounds 1 and 2 are 1D, zigzagged NiRu chains that exhibit ferromagnetic coupling between Ni(II) and Ru(III) ions through cyano bridges with J=+1.92 cm(-1), zJ'=-1.37 cm(-1), g=2.20 for 1 and J=+0.85 cm(-1), zJ'=-0.16 cm(-1), g=2.24 for 2. Compound 3 has a 1D linear chain structure that exhibits intrachain ferromagnetic coupling (J=+0.62 cm(-1), zJ'=-0.09 cm(-1), g=2.08), but antiferromagnetic coupling occurs between FeRu chains, leading to metamagnetic behavior with T(N)=2.6 K. In compound 4, two Mn(III) ions are coordinated to trans-[Ru(acac)(2)(CN)(2)](-) to form trinuclear Mn(2)Ru units, which are linked together by pi-pi stacking and weak Mn...O* interactions to form a 1D chain. Compound 4 shows slow magnetic relaxation below 3.0 K with phi=0.25, characteristic of superparamagnetic behavior. The Mn(III)...Ru(III) coupling constant (through cyano bridges) and the Mn(III)...Mn(III) coupling constant (between the trimers) are +0.87 and +0.24 cm(-1), respectively. Compound 4 is a novel single-chain magnet built from Mn(2)Ru trimers through noncovalent interactions. Density functional theory (DFT) combined with the broken symmetry state method was used to calculate the molecular magnetic orbitals and the magnetic exchange interactions between Ru(III) and M (M=Ni(II), Fe(III), and Mn(III)) ions. To explain the somewhat unexpected ferromagnetic coupling between low-spin Ru(III) and high-spin Fe(III) and Mn(III) ions in compounds 3 and 4, respectively, it is proposed that apart from the relative symmetries, the relative energies of the magnetic orbitals may also be important in determining the overall magnetic coupling in these bimetallic assemblies.

Microwave-Assisted Stepwise Synthesis and Typically Metamagnetic Behavior of a Unique Two-Dimensional Net-Based Material Based on Linear Cu(II)-Azido Chains Mediated by Discrete Cu(II) Segments

A unique two-dimensional layer-based material [Cu(μ1,1-N3)2(H2O)][CuL2] (1, L = 2-methylpyrazine-5-carboxylate) was produced by a stepwise, microwave-assisted synthesis, featuring linear Cu(II)-μ1,1-azido chains mediated by discrete CuL2 motifs. The mutual stabilization of the zero-dimensional and one-dimensional motifs in the unusual crystalline lattice of 1 is achieved by both coordination and supramolecular interactions. As a consequence, this material represents a novel copper(II)-based metamagnet resulting from the nature of the strong intrachain ferromagnetic coupling versus the weak interchain antiferromagnetic coupling.

Study of the Influence of the Bridge on the Magnetic Coupling in Cobalt(II) Complexes

Two new cobalt(II) complexes of formula [Co(2)(bta)(H(2)O)(6)](n) x 2nH(2)O (1) and [Co(phda)(H(2)O)](n) x nH(2)O (2) [H(4)bta = 1,2,4,5-benzenetetracarboxylic acid, H(2)phda = 1,4-phenylenediacetic acid] have been characterized by single crystal X-ray diffraction. Compound 1 is a one-dimensional compound where the bta(4-) ligand acts as 2-fold connector between the cobalt(II) ions through two carboxylate groups in para-conformation. Triply bridged dicobalt(II) units occur within each chain, a water molecule, a carboxylate group in the syn-syn conformation, and an oxo-carboxylate with the mu(2)O(1);kappa(2)O(1),O(2) coordination mode acting as bridges. Compound 2 is a three-dimensional compound, where the phda(2-) group acts as a bridge through its two carboxylate groups, one of them adopting the mu-O,O' coordination mode in the syn-syn conformation and the other exhibiting the single mu(2)-O'' bridging mode. As in 1, chains of cobalt(II) ions occur in 2 with a water molecule, a syn-syn carboxylate group, and an oxo-carboxylate constitute the triply intrachain bridging skeleton. Each chain is linked to other four ones through the phda(2-) ligand, giving rise to the three-dimensional structure. The values of the intrachain cobalt-cobalt separation are 3.1691(4) (1) and 3.11499(2) A (2) whereas those across the phenyl ring of the extended bta(4-) (1) and phda(2-) (2) groups are 10.1120(6) and 11.4805(69 A, respectively. The magnetic properties of 1 and 2 have been investigated in the temperature range 1.9-300 K, and their analysis has revealed the occurrence of moderate intrachain ferromagnetic couplings [J = +5.4 (1) and +2.16 cm(-1) (2), J being the isotropic magnetic coupling parameter], the magnetic coupling through the extended bta(4-) and phda(2-) with cobalt-cobalt separations larger than 10 A being negligible. The nature and magnitude of the magnetic interactions between the high-spin cobalt(II) ions in 1 and 2 are compared to those of related systems and discussed as a function of the complementarity-countercomplementarity effects of the triple bridges.