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Magnetic Measurements (magnetic + measurement)
Selected AbstractsThermal Decomposition Reactions as a Tool for the Synthesis of New Thermodynamic Metastable Modifications: Synthesis, Structures, and Properties of (Formato)nickel(II) Coordination Polymers Based on 4,4,-BipyridineEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 12 2010Jan Boeckmann Abstract The reaction of nickel formate with 4,4,-bipyridine (bipy) in aqueous solution at room temperature leads to the formation of the hydrated compound [Ni(HCO2)2(H2O)(bipy)·4H2O]n (1) reported recently. On heating, compound 1 decomposes into the new anhydrous compound of composition [Ni(HCO2)2(bipy)]n (2II), which decomposes on further heating. Interestingly, if the anhydrous compound is prepared from solution, a new modification 2I is obtained. Investigations on the stability of both forms show that modification 2I presents the thermodynamically most stable form between room and decomposition temperature, whereas modification 2II, which can only be prepared by thermal decomposition, is metastable. In the crystal structure of 2I, the Ni2+ cations are coordinated by four ,2 - anti,anti bridging formato anions and two bridging ,2 -bipy ligands in a slightly distorted octahedralgeometry. The formato anions bridge the metal cations in zigzag chains, which are further connected by ,2 - anti,anti formato anions and bipy ligands to give a three-dimensional coordination network. IR spectroscopic investigations on the metastable form 2II also indicate that all formato anions act as bridging ligands. Magnetic measurements of the hydrated and anhydrous compounds reveal different behavior with a ferromagnetic ordering for compound 2I and an antiferromagnetic ordering for compound 1. For form 2II, only Curie,Weiss paramagnetism was found. [source] Stabilization of Long Cationic EMACs by Reduction or Loss of One Metal IonEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 27 2008Rayyat H. Ismayilov Abstract The new pyrimidyl- and naphthyridyl-modulated pentapyridyltetramine ligand (H3N9 -2pm) and its linear nona- and octanickel chain complexes were successfully synthesized. The nonanickel complex [Ni9(,9 -N9 -2pm)4Cl2](PF6)2 (1) contains two fully delocalized, mixed-valence [Ni2(napy)4]3+ units. Magnetic measurements performed on the defective octanuclear complex [Ni8(,8 -N9 -2pm)4Cl2](PF6)2 (2) demonstrate that the metal chain provides a pathway of magnetic superexchange coupling over the extended metal atom chain (EMAC). (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] Synthesis, Structure and Magnetic Properties of a Novel Linear CuII -Trimer ComplexEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 22 2005Vladimir Pashchenko Abstract A new hexanuclear copper(II) sandwich complex based on two 10-membered macrocyclic phenylsiloxanolate ligands, {Cu6[(C6H5SiO2)5]2(OH)2(C10H8N2)2}·4(DMF)·3(H2O) (1), was synthesized and characterized by single-crystal X-ray diffraction and measurements of the magnetic susceptibility and isothermal magnetization. The cluster compound crystallizes in the triclinic system, space group P (No. 2), with a = 14.925(3) Å, b = 16.745(2) Å, c = 23.053(3) Å, , = 83.079(9)°, , = 84.836(13)°, , = 65.019(17)°, and Z = 2. The unit cell contains two identical molecules, each consisting of six interacting Cu2+ (S = 1/2) ions. Within the molecule, the six Cu2+ ions are arranged in two almost linear, parallel trimers. While pairs of oxygen atoms link the Cu2+ ions within the trimers, single oxygen atoms residing at the ends of the trimers provide the strongest intertrimer bonds. Magnetic measurements reveal an antiferromagnetic intratrimer exchange interaction, J/kB = 85 K, as the dominant magnetic coupling of the complex. By introducing a weak antiferromagnetic intertrimer coupling, J,/kB = 3.5 K, a satisfactory description of the magnetic behavior over a wide range of temperature and magnetic field is obtained. The departure of the model curves from the data at the lowest available temperature indicates the presence of additional, weak intra - and/or intermolecular interactions. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source] Mono-, Di- and Polymeric Calcium and Gadolinium Complexes of the Tripodal Ligand 2,2,,2,,-Nitrilotribenzoic AcidEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 4 2005Stefan Wörl Abstract Three novel carboxylate-bridged complexes incorporating the tripodal N,O ligand 2,2,,2,,-nitrilotribenzoic acid H3L of formula [CaII(H2L)(OH2)4][(H2L)]·4H2O (1), [CaII(OH2)4]-[CaII(L)(OH2)2]2·7H2O (2) and [GdIII(L)(OH2)3]2[GdIII(L)-(OH2)4]2·13H2O (3) were synthesized and characterized by X-ray crystallography. In all three complexes, the ligand H3L binds to the metal centre only by its three carboxylate donors, leaving the bridgehead nitrogen atom nonbonding. The calcium(II) ion in the monomeric complex 1 is distorted pentagonal-bipyramidal coordinated, the +1 charge of the complex cation [CaII(H2L)(OH2)4]+ is balanced by an H2L, anion and both units are connected by hydrogen bonds. The polymeric compound 2 displays a one-dimensional chain structure, in which two [CaII(L)]2, units form a dimeric structure and are connected by hydrated CaII ions. 3 contains two different [GdIII(L)(OH2)n] dimers. In one of them the two GdIII ions are linked by two monoatomic carboxylate O-bridges showing a short Gd···Gd distance of 3.99 Å. In the second, a syn - anti carboxylate 1,3-bridge with a longer Gd···Gd distance of 4.96 Å is observed. Magnetic measurements of 3 show paramagnetic behaviour with weak antiferromagnetic coupling. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source] Magnetically Controllable Silver Nanocomposite with Multifunctional Phosphotriazine Matrix and High Antimicrobial ActivityADVANCED FUNCTIONAL MATERIALS, Issue 14 2010Panagiotis Dallas Abstract A recently developed multi-functional phosphotriazine-based polymer is used as a matrix for embedding ,-Fe2O3 nanoparticles as well as a suitable chemical template for surface modification with silver nanoparticles. For the primary magnetic modification, maghemite nanoparticles are surface modified with oleic acid in order to render them organophilic and to prevent the aggregation of the nanoparticles. This aggregation could occur as the polymer synthesis, based on reaction of phosphonitrilic chlorine and 1,4-phenylenediamine, takes place in toluene. The surface active amine units of the polymer structure enable the reduction of silver cations to silver nanoparticles, which are well attached and finely dispersed on its surface. The developed nanocomposite represents one of the few magnetically controllable antibacterial agents based on silver nanoparticles. Magnetic measurements reveal the completely suppressed interactions among maghemite nanoparticles because of their perfect surface coating with an organic surfactant and fine dispersion inside the polymer matrix. This magnetic nanocomposite exhibits a high antibacterial and antifungal activity as proven by tests with nine bacterial strains and four candida (yeast genus) species. For the majority of the tested species, the minimum-inhibition concentrations are below 100,mg,L,1, which is comparable to their equivalent minimum-inhibition concentrations in colloidal silver systems. [source] Kinetically Controlled Synthesis of Hexagonally Close-Packed Cobalt Nanorods with High Magnetic CoercivityADVANCED FUNCTIONAL MATERIALS, Issue 12 2009Yaghoub Soumare Abstract High-quality monodisperse metallic cobalt nanorods are obtained by the reduction of carboxylate salts of CoII in 1,2-butanediol using a rapid, simple, and solid-template-free procedure. In this polyol process, particle shape can be controlled via the growth rate, which depends on three parameters: i) the nature of the cobalt carboxylate, ii) the temperature ramp, and iii) the basicity of the medium. Cobalt in the hexagonally close-packed phase favored the growth of anisotropic particles. Magnetic measurements of the cobalt nanorods indicate they are ferromagnetic at room temperature. They have a very high coercivity of 9.0 kOe at 140,K, much higher than that observed for wires prepared with solid templates. This can be attributed to their small mean diameter and high crystallinity. [source] Magnetic investigation of heavy metals contamination in urban topsoils around the East Lake, Wuhan, ChinaGEOPHYSICAL JOURNAL INTERNATIONAL, Issue 2 2007Tao Yang SUMMARY Magnetic measurements and heavy metal analyses were performed on 133 samples from the urban soils around the East Lake in Wuhan, China. Samples were collected from four areas with different environmental settings: a heavy industrial area well known for thermal power generation and steel works; villages located in the downwind area of the industrial area; a main road with heavy traffic and roads around the East Lake. Results show that concentrations of magnetic particle and heavy metals in urban topsoils are significantly elevated due to the input of coarser-grained magnetite from industrial (e.g. power generation and steel production) and other anthropogenic activities (e.g. vehicle emissions). Concentration-related magnetic parameters, for example, magnetic susceptibility, saturation isothermal remanent magnetization and anhysteretic remanent magnetization, significantly correlate with the concentration of heavy metals. Moreover, in terms of grain sizes, the magnetic particles of different origins can be efficiently discriminated at the studied region. Therefore, magnetic measurements provide a basis for discrimination and identification of different contamination sources, and can be used as an economic alternative to chemical analysis when mapping heavy metal contamination in urban soil around the East Lake region, Wuhan, China. [source] Concentric Sub-micrometer-Sized Cables Composed of Ni Nanowires and Sub-micrometer-Sized Fullerene Tubes,ADVANCED FUNCTIONAL MATERIALS, Issue 7 2007F. Tao Abstract Highly ordered arrays of submicrometer-sized coaxial cables composed of submicrometer-sized C60 and C70 tubes filled with Ni nanowires are successfully prepared by combining a sol,gel method with an electrodeposition process. The wall thickness of the submicrometer-sized tubes can be adjusted by the concentration of fullerenes and the immersion time. The thermal stability of the submicrometer-sized C60 tubes is studied by Raman spectroscopy and it is found that these structures can be easily decomposed to form carbon nanotubes at relatively low temperatures (above 573,K) in an alumina template. These novel coaxial cable structures have been characterized by transmission electron microscopy (TEM), high-resolution TEM (HRTEM), scanning electron microscopy (SEM), field-emission SEM (FESEM), Raman spectroscopy, elemental mapping, energy dispersive X-ray (EDX) spectroscopy, X-ray diffraction (XRD), vibrating sample magnetometer (VSM) experiments, and superconducting quantum interference device (SQUID) measurements. Magnetic measurements show that these submicrometer-sized cables exhibit enhanced ferromagnetic behavior as compared to bulk nickel. Moreover, submicrometer-sized C70/Ni cables show uniaxial magnetic anisotropy with the easy magnetic axis being parallel to the long axis of the Ni nanowires. C70/Ni cables also exhibit a new magnetic transition at ca.,10,K in the magnetization,temperature (M,T) curve, which is not observed for the analogous C60/Ni structures. The origin of this transition is not yet clear, but might be related to interactions between the Ni nanowires and C70 molecules. There is no preferred magnetization axis in submicrometer-sized C60/Ni cables, which implies that the Ni nanocrystals have different packing modes in the two composites. These different crystalline packing modes lead to different magnetic anisotropy in the two composites, although the Ni nanocrystals have the same face-centered cubic (fcc) structure in both cases. [source] Crystal Structures and Magnetic Properties of Nitronyl Nitroxide RadicalsHELVETICA CHIMICA ACTA, Issue 4 2003Alexander Zakrassov The crystal structures and magnetic properties of the nitronyl nitroxide radicals 4,5-dihydro-4,4,5,5-tetramethyl-3-oxido(1H -imidazol-1-yloxyl) (1), 4,5-dihydro-2,4,4,5,5-pentamethyl-3-oxido(1H -imidazol-1-yloxyl) (2), 2-(4-chlorophenyl)-4,5-dihydro-4,4,5,5-tetramethyl-3-oxido(1H -imidazol-1-yloxyl) (3), and 4,5-dihydro-2-(2-hydroxy-5-nitrophenyl)-4,4,5,5-tetramethyl-3-oxido(1H -imidazol-1-yloxyl) (4) are reported. Compound 1 has two polymorphic forms: the , phase is monoclinic (P21/n space group), with a single molecule in the asymmetric unit, and the , phase is monoclinic (P21/c space group), with four molecules in the asymmetric unit. In the two polymorphs, the molecules are arranged in dimers formed by hydrogen bonds of the type CH,,,ON. The crystal structure of 3 contains layers of antiparallel ribbons of molecules. Compound 4 crystallizes with solvent molecules, and an intramolecular hydrogen bond is formed between the 2-OH group of the phenyl ring and the nitroxide O-atom. Compound 4 also loses the two O-atoms of the nitroxide moiety upon heating to 90°. Magnetic measurements showed that both , and , polymorphs of 1 exhibit antiferromagnetic coupling. The best fit to the experimental data was obtained using BleanyBower's singlet-triplet model (H=,2JSaSb): J=,11.2,K for the , phase and J=,15.0,K for the , phase. Compounds 3 and 4 show no evidence for spin coupling. [source] Rock magnetism and paleomagnetic stratigraphy of forearc sediments of the Japan Trench, ODP Sites 1150 and 1151ISLAND ARC, Issue 1 2004Toshiya Kanamatsu Abstract Magnetic measurements were carried out to investigate rock magnetic properties and paleomagnetic directions of late and middle Miocene sediments recovered from the land side of the Japan Trench during the Ocean Drilling Program Leg 186. Because the low coercive component in natural remanent magnetization (NRM) normalized by anhysteretic remanent magnetization shows that the drilling-induced magnetization is severe in the sections obtained by the advanced hydraulic piston coring method, careful analyses of demagnetization of NRM using the ,demagnetization plane' were carried out to decompose the direction and intensity. Magnetostratigraphic correlation down to the upper Miocene, supplemented by biostratigraphic data, revealed that the sedimentation rates are characterized by drastic changes, with the early Pliocene having the highest rate. This high sedimentation rate is related to the subsidence of the southern deep-sea terrace of the Japan Trench. [source] The influence of mechanical alloying on the structural and physical properties of YNi4B compoundPHYSICA STATUS SOLIDI (A) APPLICATIONS AND MATERIALS SCIENCE, Issue 1 2003M. Timko Abstract We have investigated the influence of mechanical milling on structural changes, magnetic and superconducting properties of YNi4B compound. This compound crystallizes in a hexagonal structure with the P6/mmm space group. Magnetic measurements have shown that originally prepared sample exhibits superconducting behaviour below 12 K and above this temperature the sample is paramagnetic. The great decrease of intensity and broadening of diffraction lines have been detected after milling as a consequence of sample amorphisation. [source] Synthesis of MnGeO3 polycrystalline and single-crystal samples and comparative analysis of their magnetic propertiesPHYSICA STATUS SOLIDI (B) BASIC SOLID STATE PHYSICS, Issue 1 2009N. V. Sapronova Abstract MnGeO3 single crystals have been grown by a flux method. The obtained MnGeO3 is orthorhombic; a Pbca space group does not undergo any structural phase transitions in the range from room temperature to 900 °C. Magnetic measurements carried out for the first time on the MnGeO3 single crystal have revealed higher values (TN = 38 K and , = ,100 K) as compared to the data for polycrystalline samples reported in the literature (TN = 10 K and 14 K, , = ,54 K and ,46 K). These magnetic parameters for polycrystalline samples synthesized by us are close to the literature data. A Mössbauer spectrum taken at T = 300 K for a sample containing 5% Fe257O3 shows that manganese ions, Mn2+, occupy two nonequivalent positions and iron is included in a sublattice as Fe2+ and distributed among two positions substituting Mn2+. In this study, the magnetic characteristics are shown to be sensitive even to minor impurity amounts. The MnGeO3 magnetic structure and one of possible reasons causing the effect of impurities on the MnGeO3 magnetic properties are considered in the framework of a simple indirect coupling model. (© 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Magnetic and XPS studies on TbNi5,xAlx systemPHYSICA STATUS SOLIDI (C) - CURRENT TOPICS IN SOLID STATE PHYSICS, Issue 12 2004E. Burzo Abstract Magnetic measurements were performed on TbNi5,xAlx system, in the temperature range 1.7,300 K. At T = 1.7 K the saturation magnetizations are smaller than gJJ value of Tb. The nickel moments at 0 K, determined by band structure calculations are antiparallely oriented to Tb one and decrease in magnitude, being essentially null for TbNi3Al2 sample. The effective nickel moments vary from 2.10 ,B (x = 0) to , 1.10 ,B (x = 2). The XPS studies show that the Ni2p core level lines are similar to those of pure Ni, although the intensities of Ni 6 eV satellite decrease. The valence band spectra suggest an increase of the Ni3d,Al3p hybridization, when increasing Al content, in agreement with band structure calculations. (© 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Wavelet transform in denoising magnetic archaeological prospecting dataARCHAEOLOGICAL PROSPECTION, Issue 2 2007B. Tsivouraki Abstract Magnetic measurements in archaeological prospecting are often affected by cultural noise having the same high-frequency content as anomalies arising from buried antiquities. Also, in many cases the microrelief of the ground surface causes a noise that is coherent, pseudorandom and periodic. The main cause of this kind of noise is the ploughing of the earth. In this paper the efficiency of a wavelet denoising scheme is tested with respect to these types of unwanted disturbances. The proposed scheme combines the cyclospinning algorithm with a variable threshold calculated in each cycle of the algorithm. Tests on synthetic and real data show a satisfactory performance of the technique in suppressing both the white noise and the coherent noise caused by the systematic undulations of the ground surface. Copyright © 2007 John Wiley & Sons, Ltd. [source] Do Trinuclear Triplesalen Complexes Exhibit Cooperative Effects?CHEMISTRY - A EUROPEAN JOURNAL, Issue 33 2010Characterization, Enantioselective Catalytic Sulfoxidation by Chiral Trinuclear FeIII Triplesalen Complexes, Synthesis Abstract The chiral triplesalen ligand H6chand provides three chiral salen ligand compartments in a meta -phenylene arrangement by a phloroglucinol backbone. The two diastereomeric versions H6chandRR and H6chandrac have been used to synthesize the enantiomerically pure chiral complex [(FeCl)3(chandRR)] (3RR) and the racemic complex [(FeCl)3(chandrac)] (3rac). The molecular structure of the free ligand H6chandrac exhibits at the terminal donor sides the O-protonated phenol,imine tautomer and at the central donor sides the N-protonated keto,enamine tautomer. The trinuclear complexes are comprised of five-coordinate square-pyramidal FeIII ions with a chloride at the axial positions. The crystal structure of 3rac exhibits collinear chiral channels of ,11,Å in diameter making up 33.6,% of the volume of the crystals, whereas the crystal structure of 3RR exhibits voids of 560,Å3. Mössbauer spectroscopy demonstrates the presence of FeIII high-spin ions. UV/Vis spectroscopy is in accordance with a large delocalized system in the central backbone evidenced by strong low-energy shifts of the imine ,,,* transitions relative to that of the terminal units. Magnetic measurements reveal weak intramolecular exchange interactions but strong magnetic anisotropies of the FeIII ions. Complexes 3rac and 3RR are good catalysts for the sulfoxidation of sulfides providing very good yields and high selectivities with 3RR being enantioselective. A comparison of 3RR and [FeCl(salen,)] provides higher yields and selectivities but lower enantiomeric excess values (ee values) for 3RR relative to [FeCl(salen,)]. The low ee values of 3RR appeared to be connected to a strong ligand folding in 3RR, opening access to the catalytically active high-valent Fe,O species. The higher selectivity is assigned to a cooperative stabilization of the catalytically active high-valent Fe,O species through the phloroglucinol backbone in the trinuclear complexes. [source] Synthesis, X-ray Single-Crystal Structure Determination, and Magnetic Properties of [Rb(benzo[18]crown-6)]+ Salts Containing Well-Ordered Fulleride Trianions C603,,CHEMISTRY - A EUROPEAN JOURNAL, Issue 13 2009Bele Boeddinghaus Dipl.-Chem. Abstract Finally, a structure with well-resolved C603,ions and S=1/2 spin system: The two novel title compounds have clearly S=1/2 and not S=3/2 electronic states, as expected for the occupation of the triply degenerate LUMO of C60. These structures with well-ordered fullerene trianions show that the expected Jahn,Teller distortion is not observable in X-ray diffraction experiments. Crystals of the composition [Rb(benzo[18]crown-6)]3[,3 -C60](C7H8)(C3H7NO)4.5 (1) and [Rb(benzo[18]crown-6)]3[C60](C3H7NO)5.33(C4H8O)1.66 (2) were synthesized by reduction of C60 with elemental rubidium in a mixture of dimethylformamide/tetrahydrofuran in the presence of benzo[18]crown-6. X-ray single-crystal structure determinations reveal well-ordered C60 trianions in both compounds. In contrast to previously reported structures of compounds containing C603, ions the present structure refinements allow the description of the buckyballs with good resolution (R1/wR2 for I>2,(I) (all data) are 0.030/0.069 (0.051/0.071) and 0.042/0.101 (0.076/0.108) for 1 and 2, respectively). In 1 the C603, unit coordinates in an ,3 -fashion to one Rb atom, whose coordination sphere is completed by one benzo[18]crown-6 and one dimethylformamide molecule. In 2 no coordination of the alkali metal atom to the C60 trianion is observed. Magnetic measurements for 1 reveal a magnetic moment of 1.74,,B, as expected for an isolated S=1/2 spin system. The high-quality data of the present studies allowed a comparison of structural details of C603, ions with other C60n, units (n=0, 2, 3) and a discussion of the structural Jahn,Teller distortions. [source] Tuning the Magnetic Properties of LixCrTi0.25Se2 (0.03,x,0.7) by Directed Deintercalation of LithiumCHEMISTRY - A EUROPEAN JOURNAL, Issue 16 2008Malte Behrens Dr. Abstract X-ray diffraction (XRD), in situ energy-dispersive X-ray diffraction (EDXRD), X-ray absorption near-edge structure (XANES), extended X-ray absorption fine structure (EXAFS), and magnetic measurements were applied to investigate the effects of lithium deintercalation on pseudolayered Li0.70CrTi0.25Se2. A detailed picture of structural changes during the deintercalation process was obtained by combining the results of EDXRD and EXAFS. Removal of Li from the host,guest complex leads to anisotropic contraction of the unit cell with stronger impact on the c axis, which is the stacking axis of the layers. The EDXRD experiments evidence that the shrinkage of the lattice parameters with decreasing xLi in LixCrTi0.25Se2 is nonlinear in the beginning and then becomes linear. Analysis of the EXAFS spectra clearly shows that the Cr/TiSe distances are affected in a different manner by Li removal. The CrSe bond lengths decrease, whereas the TiSe bonds lengthen when the Li content is reduced, which is consistent with XRD data. Magnetic measurements reveal a change from predominantly antiferromagnetic exchange (,p=,300,K) interactions for the pristine material to ferromagnetic exchange interactions (,=25,K) for the fully intercalated material. Thus, the magnetic properties can be altered under ambient conditions by directed adjustment of the dominant magnetic exchange. The unusual magnetic behavior can be explained on the basis of the variation of the metal,metal distances and the Cr-Se-Cr angles with x, which were determined by Rietveld refinements. Owing to competing ferromagnetic and antiferromagnetic exchange interactions and disorder, the magnetic ground state of the intercalated materials is characterized by spin-glass or spin-glass-like behavior. [source] Fe2 and Fe4 Clusters Encapsulated in Vacant Polyoxotungstates: Hydrothermal Synthesis, Magnetic and Electrochemical Properties, and DFT CalculationsCHEMISTRY - A EUROPEAN JOURNAL, Issue 10 2008Céline Pichon Abstract While the reaction of [PW11O39]7, with first row transition-metal ions Mn+ under usual bench conditions only leads to monosubstituted {PW11O39M(H2O)} anions, we have shown that the use of this precursor under hydrothermal conditions allows the isolation of a family of novel polynuclear discrete magnetic polyoxometalates (POMs). The hybrid asymmetric [FeII(bpy)3][PW11O39Fe2III(OH)(bpy)2],12,H2O (bpy=bipyridine) complex (1) contains the dinuclear {Fe(,-O(W))(,-OH)Fe} core in which one iron atom is coordinated to a monovacant POM, while the other is coordinated to two bipyridine ligands. Magnetic measurements indicate that the FeIII centers in complex 1 are weakly antiferromagnetically coupled (J=,11.2,cm,1, H=,JS1S2) compared to other {Fe(,-O)(,-OH)Fe} systems. This is due to the long distances between the iron center embedded in the POM and the oxygen atom of the POM bridging the two magnetic centers, but also, as shown by DFT calculations, to the important mixing of bridging oxygen orbitals with orbitals of the POM tungsten atoms. The complexes [Hdmbpy]2[FeII(dmbpy)3]2[(PW11O39)2Fe4IIIO2(dmbpy)4],14,H2O (2) (dmbpy=5,5,-dimethyl-2,2,-bipyridine) and H2[FeII(dmbpy)3]2[(PW11O39)2Fe4IIIO2(dmbpy)4],10,H2O (3) represent the first butterfly-like POM complexes. In these species, a tetranuclear FeIII complex is sandwiched between two lacunary polyoxotungstates that are pentacoordinated to two FeIII cations, the remaining paramagnetic centers each being coordinated to two dmbpy ligands. The best fit of the ,MT=f(T) curve leads to Jwb=,59.6,cm,1 and Jbb=,10.2,cm,1 (H=,Jwb(S1S2+S1S2*+S1*S2+S1*S2*),Jbb(S2S2*)). While the Jbb value is within the range of related exchange parameters previously reported for non-POM butterfly systems, the Jwb constant is significantly lower. As for complex 1, this can be justified considering FewO distances. Finally, in the absence of a coordinating ligand, the dimeric complex [N(CH3)4]10[(PW11O39FeIII)2O],12,H2O (4) has been isolated. In this complex, the two single oxo-bridged FeIII centers are very strongly antiferromagnetically coupled (J=,211.7,cm,1, H=,JS1S2). The electrochemical behavior of compound 1 both in dimethyl sulfoxide (DMSO) and in the solid state is also presented, while the electrochemical properties of complex 2, which is insoluble in common solvents, have been studied in the solid state. [source] From 1D Polymeric Chain to Two-fold Parallel Interpenetration of (4,4) Net: Synthesis and Characterization of Two New Copper(II) Complexes Derived from Highly Polydentate Aminopolycarboxylate LigandCHINESE JOURNAL OF CHEMISTRY, Issue 7 2008Ya-Pan WU Abstract Two new copper(II) polymers, {[Cu2(egta)(bpe)(H2O)2]·H2O}n (1) and {[Cu2(egta)(bipy)(H2O)2]·5H2O}n(2), [H4egta=3,12-bis(carboxymethyl)-6,9-dioxa-3,12-diazatetradecanedioic acid, bpe=1,2-bis(4-pyridyl)ethane, bipy4,4,-bipyridyl] have been synthesized and structurally characterized by single-crystal X-ray diffraction, elemental analysis, IR spectra and TG analysis. The structure determination reveals that both 1 and 2 crystallize in a monoclinic system, space group P21/c. Complex 1 exhibits a two-fold parallel interpenetration of (4,4) net framework consisting of 1D zigzag chains interlocked together through hydrogen bonding interaction. However, the meso-helix chains of 2 are packed to form 2D supramolecular structures. Interestingly, in 2, the host frameworks encapsulate a unique pentamer water cluster and are further connected into 1D tapes by water-water hydrogen bonding interaction. Magnetic measurements reveal that there is a weak ferromagnetic interaction between the adjacent Cu(II) ions in 1. [source] Tetranuclear Manganese Complexes with [MnII4] and [MnII2MnIII2] Units: Syntheses, Structures, Magnetic Properties, and DFT Study,EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 28 2010Lucjan B. Jerzykiewicz Abstract Two tetranuclear manganese compounds, [Mn4(,3,,2 -L)4Br4(LH)4] (1) and [Mn4(,3,,2 -L)2(,,,2 -L)4L2Br2] (2), with cubane and defect dicubane-like cores were synthesized and characterized by single-crystal X-ray diffraction, magnetic measurements, and DFT calculations (LH = 2-methoxyethanol). The magnetic properties of the resulting [Mn4] building blocks are presented and discussed in detail. In particular, in 2 the MnIII,O,MnIII angle 103.12(8)° is the largest observed to date for such a system. The conjunction of antiferromagnetic and ferromagnetic interactions within the tetranuclear mixed-valent MnII2MnIII2 complexes results in an unusual ST = 1 ground state. [source] A ,3 -Alkoxo-Bridged Tetranuclear [Cu4L2] Copper(II) Complex of a Hexadentate N2O4 Donor Ligand with a [6 + 0] Cu4O4 Cubane Core: Synthesis, Crystal Structure, and Magnetic PropertiesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 22 2010Dipankar Maity Abstract A novel hexacoordinating non-Schiff base ligand (H4L) with N2O4 donor atoms has been synthesized by simple Mannich reactions. The use of this ligand with Cu(ClO4)2·6H2O in different molar ratios as well as pH leads to the formation of a mononuclear species and a tetranuclear CuII complex possessing a cubane [Cu4L2] core with almost equal Cu···Cu separation. In the presence of an excess amount of copper(II) ions and triethylamine at reflux, the mononuclear [CuH2L] species can be converted into the tetranuclear one, whereas the reverse process was not observed even after prolonged reaction time. Both the complexes have been characterized by single-crystal X-ray diffraction and magnetic measurements. Magnetic studies reveal that complex 1 displays a paramagnetic Curie-type behavior whereas 2 displays a singlet-spin ground state induced by strong intramolecular antiferromagnetic interactions. [source] Two New Iron(II) Spin-Crossover Complexes with N4O2 Coordination Sphere and Spin Transition around Room TemperatureEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 36 2009Birgit Weber Abstract The reaction of iron(II) acetate with the tetradentate Schiff base like ligand H2L1 {[3,3,]-[4,5-dihydroxy-1,2-phenylenebis(iminomethylidyne)bis(2,4-pentanedion)]} leads to the formation of the complex [FeL1(MeOH)]. Reaction of this complex with pyridine (py) or N,N,-dimethylaminopyridine (dmap) leads to the two N4O2 -coordinated complexes [FeL1(py)2]·py (1) and [FeL1(dmap)2]·MeOH·0.5dmap (2). Both complexes are spin-crossover compounds that were characterised by using magnetic measurements, X-ray crystallography and temperature-dependent 1H NMR spectroscopy. Special attention was given to the role of the two hydroxy groups on the phenyl ring in the formation of a hydrogen-bonding network and the influence of this network on the spin-transition properties. Although only a gradual spin crossover was observed for both complexes, the transition temperature was shifted to higher temperatures relative to that of the complexes with no additional hydroxy groups at the Schiff base like ligand. The hydrogen-bonding network was responsible for this effect.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] Quenching the Hysteresis in Single Crystals of a 1D Chain Iron(II) Spin Crossover ComplexEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 19 2008Birgit Weber Abstract The unusual grinding effects observed in the 1D spin crossover polymer [FeL(bipy)]n (1), with L being a tetradentate N2O22, coordinating Schiff base type ligand {(3,3,)-[1,2-phenylenebis(iminomethylidyne)]bis(2,4-pentanedionato)(2,)- N,N,,O2,O2,} and bipy = 4,4,-bipyridine, are investigated using magnetic measurements, X-ray powder diffraction and optical reflectivity studies. The observed behaviour can be explained when solvent effects are taken into account. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] Synthesis and Crystal Structure of Mercury-Substituted Type-I Clathrates A8Hg4Sn42 (A = K, Rb, Cs)EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 4 2008Andreas Kaltzoglou Abstract The mercury-substituted type-I clathrates A8Hg4Sn42,with A = K, Rb or Cs, were obtained by fusion of the pure elements at high temperatures. The crystal structures of the compounds were refined from single-crystal X-ray diffraction data. They crystallize in the space group Pmn (No. 223), Z = 1 with a = 12.1255(4) Å for K8Hg4Sn42 (1), a = 12.1838(4) Å for Rb8Hg4Sn42 (2) and a = 12.2130(4) Å for Cs8Hg4Sn42 (3). The 3D framework of four-bonded atoms defines two types of polyhedral cages of different size that are fully occupied by the alkali-metal atoms. All three compounds are considered as formally charge-balanced Zintl phases without any homogeneity range. Differential thermal analysis (DTA) indicates that the stability of the clathrates significantly depends on the size of the encaged cations. The thermal stability of the title compounds and the binary phases A8Sn44 (A = K, Rb, Cs) is discussed. Temperature-dependent magnetic measurements for compound 3 show also the expected diamagnetic behaviour. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] [CuII4] Clusters From the Self-Assembly of Two Imidazolidinyl 2-Phenolate-Bridged [CuII2] Units: The Role of the Chloride BridgeEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 12 2007Alok Ranjan Paital Abstract A new family of tetracopper clusters [Cu4(,4 -X)L2]ClO4·nH2O (1a,c) [X = Cl, Br, I; n = 12, 2, 2; H3L = 2-(2,-hydroxyphenyl)-1,3-bis[4-(2-hydroxyphenyl)-3-azabut-3-enyl]-1,3-imidazolidine] have been synthesised and characterised. The X-ray crystal structure of 1a reveals that the template action of the spherical Cl, anion (,4 -Cl,), which features a unique rectangular planar bridging mode, is responsible for the self-assembly of two [Cu2L]+ units in complex 1a. In this family of complexes the spherical halides serve as templates to assemble the dimeric unit into tetrameric complexes, which gives an insight into the role of the halide bridge in tetranuclear complex formation. The capacity of this bridge to mediate magnetic coupling has been examined by bulk magnetic measurements for complex 1a. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] Chemical and Electrochemical Behaviours of a New Phenolato-Bridged Complex [(L)MnIIMnII(L)]2+.EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 21 2006Dinuclear Mono-µ-Oxido [(L)MnIII(µ-O)MnIII/IV(L)]2+/3+ Species, Pathways to Mononuclear Chlorido [(L)MnII/III/IVCl]0/1/2+ Abstract The X-ray structure of a new dinuclear phenolato-bridged Mn2II complex abbreviated as [(L)MnMn(L)]2+ (1), where LH is the [N4O] phenol containing ligand N,N -bis(2-pyridylmethyl)- N, -salicylidene-ethane-1,2-diamine ligand, is reported. A J value of ,3.3 cm,1 (H = ,J,1·,2) was determined from the magnetic measurements and the 9.4 GHz EPR spectra of both powder and frozen acetonitrile solution samples were analyzed with temperature. The cyclic voltammetry of 1 displays a reversible anodic wave at E1/2 = 0.46 V vs. SCE associated with the two-electron oxidation of 1 yielding the dinuclear Mn2III complex [(L)MnMn(L)]4+ (2). The easy air oxidation of 1 gives the mono-,-oxido Mn2III complex [(L)Mn(, - O)Mn(L)]2+ (3). A rational route to the formation of the mixed-valence Mn2III,IV complex [(L)Mn(, - O)Mn(L)]3+ (4) starting from 1 by bulk electrolysis at EP = 0.75 V vs. SCE in the presence of one equiv. of base per manganese ion is also briefly reported. Addition of chloride ions to 1 led to the cleavage of the phenolato bridges to give the mononuclear MnII complex [(L)MnCl] (5). Cyclic voltammetry of 5 displays two reversible anodic waves at E1/2 = 0.21 and E1/2 = 1.15 V vs. SCE, assigned to the two successive one-electron abstractions giving the MnIII and MnIV species [(L)MnCl]+ (6) and [(L)MnCl]2+ (7), respectively. The electronic signatures from UV/Visible and EPR spectroscopy of the electrochemically prepared samples of 6 and 7 confirmed the respective oxidation states. For instance, 7 displays a broad and intense absorption band characteristic of a phenolato to MnIV charge-transfer transition at 690 nm (2000 M,1,cm,1) and its 9.4 GHz EPR spectrum shows a strong transition at g = 5.2 consistent with a rhombically distorted S = 3/2 system with a zero-field splitting dominating the Zeeman effect. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source] Synthesis, Structure and Magnetic Properties of a Tetranuclear Copper(II) Complex on the Basis of a 2-Substituted Glucopyranoside Schiff Base Ligand,EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 17 2006Anja Burkhardt Abstract Condensation of a derivatized 2-aminoglucose fragment with salicylaldehyde affords the new sugar-based Schiff base ligand benzyl 4,6- O -benzylidene-2-deoxy-2-salicylideneamino-,- D -glucopyranoside (H2L). The reaction of the dibasic ligand H2L with [Cu(CH3COO)2]·H2O leads to the formation of the tetranuclear copper(II) complex [{Cu(L)}4] (3) by a self-assembly process. The X-ray structural analysis of complex 3 which crystallizes together with two molecules of chloroform and one molecule of ethanol in the space group P212121 revealed for all copper atoms a NO3 coordination environment with a square-planar geometry. The tetranuclear molecule 3 consists of four chiral building blocks {Cu(L)} with the rare 2,3-coordination of the trans -configured donor atoms of the sugar backbone. The observed coordination mode of the building blocks exemplifies how chitosan-derived polysaccharide ligands can act as a chiral support for transition-metal complexes. The C-3 alcoholate oxygen atoms of the carbohydrate unit is bridging adjacent {Cu(L)} moieties resulting in an eight-membered Cu4O4 ring with a boat-like conformation. Temperature-dependent magnetic measurements of 3 indicate moderate antiferromagnetic interactions between the four copper(II) ions with a coupling constant of J = ,130 cm,1.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source] A Zig-Zag [MnII4] Cluster from a Novel Bis(,-diketonate) LigandEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 10 2006Guillem Aromí Abstract A new ligand, H5L3, has been synthesized featuring seven linearly arranged oxygen donors in form of two 1,3-diketone and three phenol groups. The X-ray structure of H5L3 unveils a rare case where one of the diketones is in the enolic form and the other one in the bis(carbonyl) form. This structure is shown by 1H NMR to persist in solution. Reaction of H5L3 with Mn(AcO)2 in pyridine leads to the novel tetranuclear cluster [Mn4(H2L3)2(OAc)2(py)5] (1), which displays an unusual core in form of a zig-zag chain. Bulk magnetic measurements revealed the existence of weak antiferromagnetic coupling within the molecule. Numerical fits to a model described by the Hamiltonian H = ,2J1(S1S2 + S3S4) , 2J2(S2S3) yield coupling constants of J1 = ,2.23 cm,1, J2 = ,0.85 cm,1 and g = 2.08. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source] Syntheses, Crystal Structures and Magnetic Properties of Carboxylato-Bridged Polymeric Networks of MnIIEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 2 2006Subal Chandra Manna Abstract Three new carboxylato-bridged polymeric networks of MnII having,molecular formula [Mn(ox)(dpyo)]n (1), {[Mn2(mal)2(bpee)(H2O)2]·0.5(bpee)·0.5(CH3OH)}n (2) and {[Mn3(btc)2(2,2,-bipy)2(H2O)6]·4H2O}n (3) [dpyo, 4,4,-bipyridine N,N,-dioxide; bpee, trans -1,2 bis(4-pyridyl)ethylene; 2,2,-bipy, 2,2,-bipyridine; ox = oxalate dianion; mal = malonate dianion; btc = 1,3,5-benzenetricarboxylate trianion] have been synthesized and characterized by single-crystal X-ray diffraction studies and low temperature magnetic measurements. Structure determination of complex 1 reveals a covalent bonded 2D network containing bischelating oxalate and bridging dpyo; complex 2 is a covalent bonded 3D polymeric architecture, formed by bridging malonate and bpee ligands, resulting in an open framework with channels filled by uncoordinated disordered bpee and methanol molecules. Whereas complex 3, comprising btc anions bound to three metal centers, is a 1D chain which further extends its dimensionality to 3D via - and H-bonding interactions. Low temperature magnetic measurements reveal the existence of weak antiferromagnetic interaction in all these complexes. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source] A Crystalline Phase Transition and Optical Properties in a CoIICuII Oxamato-Bridged Ferrimagnetic ChainEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 24 2005Cynthia L. M. Pereira Abstract The compound [CoCu(opba)(DMSO)3] (1) [opba = ortho -phenylenebis(oxamato)] has been synthesized and characterized. Its crystal structure has been analyzed by X-ray diffraction techniques at 100 and 298 K. A structural phase-transition has been detected at around 150 K. An orthorhombic crystalline system is found at both temperatures, with very similar unit-cell dimensions. At room temperature 1 crystallizes in the Pnam space group (, -1 phase), with a = 7.6712(2), b = 14.8003(3), c = 21.0028(5) Å, and Z = 4, whereas at low temperature it crystallizes in the Pna21 space group (, -1 phase), with a = 7.3530(2), b = 14.5928(4), c = 21.0510(7) Å, and Z = 4. Both crystalline phases consist of linearly ordered bimetallic chains with the [Cu(opba)]2, units tied by CoII ions to form a one-dimensional system. The DMSO molecules in , -1, which are coordinated to either CuII or CoII, are disordered. At low temperature, a small reorganization of the CuII and CoII environments is observed. The origin of this phase transition, which is completely reversible, is the modification of the crystalline packing with the temperature. Linear birefringence measurements were done on single crystals in the 100,300 K temperature range. Around 150 K, the linear birefringence curve shows an inflexion that is interpreted as being related to the conversion of ,-1 into , -1. Both dc and ac magnetic measurements were performed on the polycrystalline sample. The results reveal a one-dimensional ferrimagnetic behavior. Single crystal optical characterization at room temperature shows that 1 presents a very strong dichroism superposed on the linear birefringence. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source] | |||||||||||||||||||