Effect of graphene on the key electrical, optical, and magnetic properties of polymethylmethacrylate: a study based on molecular modeling.

CONTEXT: In this work, a new polymeric structure was designed consisting of a nanometric sheet of graphene (G) and a polymethylmethacrylate (PMMA) repeat unit, which was designated as PMMA-G. Three degrees of polymerization of PMMA-G were considered: monomer (PMMA-G1), dimer (PMMA-G2), and trimer (PMMA-G3). The effect of incorporating a nanometric sheet of graphene into the molecular structure of PMMA on the modification of some of its main optical, magnetic, and electrical properties was investigated. Currently, the study presented here is of great relevance since various areas of technology require new materials with specific properties for the development of new devices. The results of our study reveal that the dielectric constant of PMMA is reduced when graphene is incorporated. However, a percentage increase of 14.48% in the refractive index of PMMA when graphene is inserted to form the nanocomposite is observed. It is found that the absolute value of molar magnetic susceptibility of PMMA increases considerably when reinforced with graphene. Finally, when reinforcing PMMA with graphene to obtain the PMMA-G nanocomposite, the electrical resistivity increases by almost an order of magnitude. METHODS: We used computational tools under Materials Studio (MS) software. We built a PMMA molecule with three degrees of polymerization, graphene sheet, and polymethylmethacrylate-graphene composite (PMMA-G) was built also with three degrees of polymerization using a concentration of 50% graphene over the PMMA polymer. For each structure, we used computational code DMol3 of MS, which is based on the Density Functional Theory, and the geometry optimization process was carried out to obtain the most stable structures. Finally, using the connectivity indices method together with topological properties of the molecular structures, implemented in Synthia computational code of MS software, we calculated the dielectric constant, magnetic susceptibility, refractive index, and electrical resistivity, for pure PMMA and PMMA-G structures for their three degrees of polymerization. The results were analyzed, and the changes in these properties were discussed in terms of the effect of an electric and magnetic field on the molecular structures of PMMA-G with respect to PMMA.

Crystal structure and cryomagnetic study of a mononuclear erbium(III) oxamate inclusion complex.

The synthesis, crystal structure and magnetic properties of an oxamate-containing erbium(III) complex, namely, tetrabutylammonium aqua[N-(2,4,6-trimethylphenyl)oxamato]erbium(III)-dimethyl sulfoxide-water (1/3/1.5), (C16H36N)[Er(C11H12NO3)4(H2O)]·3C2H6OS·1.5H2O or n-Bu4N[Er(Htmpa)4(H2O)]·3DMSO·1.5H2O (1), are reported. The crystal structure of 1 reveals the occurrence of an erbium(III) ion, which is surrounded by four N-phenyl-substituted oxamate ligands and one water molecule in a nine-coordinated environment, together with one tetrabutylammonium cation acting as a counter-ion, and one water and three dimethyl sulfoxide (DMSO) molecules of crystallization. Variable-temperature static (dc) and dynamic (ac) magnetic measurements were carried out for this mononuclear complex, revealing that it behaves as a field-induced single-ion magnet (SIM) below 5.0 K.

Utilization of Additive Manufacturing Techniques for the Development of a Novel Scaffolds with Magnetic Properties for Potential Application in Enhanced Bone Regeneration.

This study focuses on designing and evaluating scaffolds with essential properties for bone regeneration, such as biocompatibility, macroporous geometry, mechanical strength, and magnetic responsiveness. The scaffolds are made using 3D printing with acrylic resin and iron oxides synthesized through solution combustion. Utilizing triply periodic minimal surfaces (TPMS) geometry and mask stereolithography (MSLA) printing, the scaffolds achieve precise geometrical features. The mechanical properties are enhanced through resin curing, and magnetite particles from synthesized nanoparticles and alluvial magnetite are added for magnetic properties. The scaffolds show a balance between stiffness, porosity, and magnetic responsiveness, with maximum compression strength between 4.8 and 9.2 MPa and Young's modulus between 58 and 174 MPa. Magnetic properties such as magnetic coercivity, remanence, and saturation are measured, with the best results from scaffolds containing synthetic iron oxides at 1% weight. The viscosity of the mixtures used for printing is between 350 and 380 mPas, and contact angles between 90° and 110° are achieved. Biocompatibility tests indicate the potential for clinical trials, though further research is needed to understand the impact of magnetic properties on cellular interactions and optimize scaffold design for specific applications. This integrated approach offers a promising avenue for the development of advanced materials capable of promoting enhanced bone regeneration.

Scientific and technological analysis of exchange-spring magnets: Applications and trends.

In this work, a bibliometric study was carried out to perform a scientific and technological analysis of exchange-spring magnets, an alternative permanent magnet synthesized by reducing or eliminating the use of critical raw materials, such as rare earths. The bibliometric analysis utilized the Scopus database, Orbit-Intellixir, VOSviewer, Orbit-Intelligence and Loglet Lab 4 software for maturity analysis, keyword network representations, charts and graphs for scientific articles and/or patents. A special analysis was performed on nanocomposite and thin-films systems based on Nd-Fe-B, SmCo5 and Mn-Al-C alloys, either mixed or layered with a soft magnetic phase, where relevant information on their magnetic parameters was compilated in tables, highlighting the nanostructured systems that have been exhibited the best permanent magnet properties. The bibliometric analysis revealed that the primary production of scientific articles is concentrated in industrialized countries, and they are predominantly published in journals dedicated to magnetism. A patents analysis showed that Nissan motors is by far the main applicant, with most of its patents is focused on technological domains related to electrical machinery, apparatus, energy and metallurgy. On the other hand, the S-curve of maturity for scientific articles indicated that the study of exchange-spring magnets is entering a mature state. In contrast, patent production, following a bi-logistic model, is in a saturation stage for the second S-curve. Maturity analyses, employing S-curve, bi-logistic and multi-logistic models, were performed on nanocomposites and thin films based on Nd-Fe-B, SmCo5 and Mn-Al-C alloys, respectively. We found that the investigation in Nd-Fe-B-based alloys is close to enter to a scientific saturation stage, while an average growth stage is observed for the SmCo5 and Mn-Al-C-based alloys. This suggests that research on alternative magnets, capable of fulfilling technological applications where a Nd-Fe-B magnets are commonly used, is a topic of significant interest.

Longitudinal Spin Seebeck Effect Thermopiles Based on Flexible Co-Rich Amorphous Ribbons/Pt Thin-Film Heterostructures.

Thermoelectric phenomena, such as the Anomalous Nernst and Longitudinal Spin Seebeck Effects, are promising for sensor applications in the area of renewable energy. In the case of flexible electronic materials, the request is even larger because they can be integrated into devices having complex shape surfaces. Here, we reveal that Pt promotes an enhancement of the thermoelectric response in Co-rich ribbon/Pt heterostructures due to the spin-to-charge conversion. Moreover, we demonstrated that the employment of the thermopiles configuration in this system increases the induced thermoelectric current, a fact related to the considerable decrease in the electric resistance of the system. By comparing present findings with the literature, we were able to design a flexible thermopile based on LSSE without the lithography process. Additionally, the thermoelectric voltage found in the studied flexible heterostructures is comparable to the ones verified for rigid systems.

Annealing effects on the magnetic and magnetotransport properties of iron oxide nanoparticles self-assemblies.

In magnetic tunnel junctions based on iron oxide nanoparticles the disorder and the oxidation state of the surface spin as well as the nanoparticles functionalization play a crucial role in the magnetotransport properties. In this work, we report a systematic study of the effects of vacuum annealing on the structural, magnetic and transport properties of self-assembled ∼10 nm Fe3O4nanoparticles. The high temperature treatment (from 573 to 873 K) decomposes the organic coating into amorphous carbon, reducing the electrical resistivity of the assemblies by 4 orders of magnitude. At the same time, the 3.Fe2+/(Fe3++Fe2+) ratio is reduced from 1.11 to 0.13 when the annealing temperature of the sample increases from 573 to 873 K, indicating an important surface oxidation. Although the 2 nm physical gap remains unchanged with the thermal treatment, a monotonous decrease of tunnel barrier width was obtained from the electron transport measurements when the annealing temperature increases, indicating an increment in the number of defects and hot-spots in the gap between the nanoparticles. This is reflected in the reduction of the spin dependent tunneling, which reduces the interparticle magnetoresistance. This work shows new insights about influence of the nanoparticle interfacial composition, as well their the spatial arrangement, on the tunnel transport of self-assemblies, and evidence the importance of optimizing the nanostructure fabrication for increasing the tunneling current without degrading the spin polarized current.

Tunable Magnetic Properties of Interconnected Permalloy Nanowire Networks.

In this study, we investigate the magnetic properties of interconnected permalloy nanowire networks using micromagnetic simulations. The effects of interconnectivity on the hysteresis curves, coercivity, and remanence of the nanowire networks are analyzed. Our results reveal intriguing characteristics of the hysteresis curves, including nonmonotonic behaviors of coercivity as a function of the position of horizontal nanowires relative to vertical nanowires. By introducing horizontal nanowires at specific positions, the coercivity of the nanowire networks can be enhanced without altering the material composition. The normalized remanence remains relatively constant regardless of the position of the horizontal wires, although it is lower in the interconnected nanowire arrays compared to nonconnected arrays. These findings provide valuable insights into the design and optimization of nanowire networks for applications requiring tailored magnetic properties.

Assessing heavy metal pollution load index (PLI) in biomonitors and road dust from vehicular emission by magnetic properties modeling.

Vehicular traffic occupies a significant place among the sources of air pollution, due to population and urban growth that has led to an excessive increase in the vehicle fleet worldwide, and in Costa Rica as well. Vehicle emissions generate greenhouse gases (GHGs), particulate matter (PM), and heavy metals (HMs), due to combustion products from fossil-fuel engines, tire wear, and brake linings. HMs are important because they cannot be degraded or destroyed naturally; however, they can be diluted by physicochemical agents and be incorporated into trophic chains where they can be bioaccumulated causing significant negative effects on human well-being and ecological quality. This study aimed to assess the HM pollution load in biomonitors and road dust from vehicular emissions by chemical analyses and magnetic properties modeling. For this purpose, chemical and magnetic property analyses were carried out on samples of road dust and leaves of Cupressus lusitanica Mill. and Casuarina equisetifolia L., which were sampled during 2 different years in the Greater Metropolitan Area of Costa Rica known as GAM. Contamination factor (CF) and pollution load index (PLI) results showed significant metal pollution in some of the study sites. Contamination by the metals V, Cr, and Zn was most commonly present in the biomonitors, and for road dust, they were Cr, Zn, and Pb. The PLI estimates obtained with the validated support vector machine (SVM) magnetic properties models were consistent (sensitivity, specificity, and precision) with those obtained by chemical analysis, demonstrating the feasibility of this method for the identification of this index of contamination.

Static and Dynamic Magnetic Properties of Fe3O4 Nanotubes.

In this paper, our objective was to investigate the static and dynamic magnetic properties of Fe3O4 nanotubes that are 1000 nm long, by varying the external radius and the thickness of the tube wall. We performed a detailed numerical analysis by simulating hysteresis curves with an external magnetic field applied parallel to the axis of the tubes (along the z-axis). Our findings indicate that nanotubes with an external radius of 30 nm exhibit non-monotonic behavior in their coercivity due to a change in the magnetization reversal mechanism, which was not observed in nanotubes with external radii of 80 nm. Additionally, we explored the dynamic susceptibility of these nanotubes and found that the position and number of resonance peaks can be controlled by manipulating the nanotube geometry. Overall, our study provides valuable insights into the behavior of Fe3O4 nanotubes, which can aid in the design and improvement in pseudo-one-dimensional technological devices.

Anomalous Nernst Effect in Flexible Co-Based Amorphous Ribbons.

Fe3Co67Cr3Si15B12 ribbons with a high degree of flexibility and excellent corrosion stability were produced by rapid quenching technique. Their structural, magnetic, and thermomagnetic (Anomalous Nernst Effect) properties were studied both in an as-quenched (NR) state and after stress annealing during 1 h at the temperature of 350 °C and a specific load of 230 MPa (AR). X-ray diffraction was used to verify the structural characteristics of our ribbons. Static magnetic properties were explored by inductive technique and vibrating sample magnetometry. The thermomagnetic curves investigated through the Anomalous Nernst Effect are consistent with the obtained magnetization results, presenting a linear response in the thermomagnetic signal, an interesting feature for sensor applications. Additionally, Anomalous Nernst Effect coefficient SANE values of 2.66µV/K and 1.93µV/K were estimated for the as-quenched and annealed ribbons, respectively. The interplay of the low magnetostrictive properties, soft magnetic behavior, linearity of the thermomagnetic response, and flexibility of these ribbons place them as promising systems to probe curved surfaces and propose multifunctional devices, including magnetic field-specialized sensors.

Presence of Induced Weak Ferromagnetism in Fe-Substituted YFexCr1-xO3 Crystalline Compounds.

Fe-substituted YFexCr1-xO3 crystalline compounds show promising magnetic and multiferroic properties. Here we report the synthesis and characterization of several compositions from this series. Using the autocombustion route, various compositions (x = 0.25, 0.50, 0.6, 0.75, 0.9, and 1) were synthesized as high-quality crystalline powders. In order to obtain microscopic and atomic information about their structure and magnetism, characterization was performed using room temperature X-ray diffraction and energy dispersion analysis as well as temperature-dependent neutron diffraction, magnetometry, and 57Fe Mössbauer spectrometry. Rietveld analysis of the diffraction data revealed a crystallite size of 84 (8) nm for YFeO3, while energy dispersion analysis indicated compositions close to the nominal compositions. The magnetic results suggested an enhancement of the weak ferromagnetism for the YFeO3 phase due to two contributions. First, a high magnetocrystalline anisotropy was associated with the crystalline character that favored a unique high canting angle of the antiferromagnetic phase (13°), as indicated by the neutron diffraction analysis. This was also evidenced by the high magnetic hysteresis curves up to 90 kOe by a remarkable high critical coercivity value of 46.7 kOe at room temperature. Second, the Dzyaloshinskii-Moriya interactions between homogenous and heterogeneous magnetic pairs resulted from the inhomogeneous distribution of Fe3+ and Cr3+ ions, as indicated by 57Fe Mössbauer studies. Together, these results point to new methods of controlling the magnetic properties of these materials.

Hollow Iron Oxide Nanospheres Obtained through a Combination of Atomic Layer Deposition and Electrospraying Technologies.

In the present study, we report on the successful synthesis of hollow iron oxide nanospheres. The hollow Fe3O4 nanospheres were synthesized following a four-step procedure: electrospraying spherical PVP particles, coating these particles with alumina (Al2O3) and hematite (Fe2O3) through atomic layer deposition and, finally, a thermal reduction process to degrade the polymer (PVP) and convert hematite (Fe2O3) into magnetite (Fe3O4). A structural analysis using X-ray diffraction (XRD) confirmed the effectiveness of the thermal reduction process. A morphological analysis confirmed that the four-step procedure allowed for the obtainment of hollow iron oxide nanospheres, even though the reduction process caused a contraction in the diameter of the particles of almost 300 nm, but did not affect the thickness of the walls of the hollow spheres that remained at approximately 15 nm. Magnetic properties of the hollow iron oxide nanospheres enable their use in applications where the agglomeration of magnetic nanostructures in liquid media is commonly not allowed, such as in drug encapsulation and delivery.

Lanthanide SMMs Based on Belt Macrocycles: Recent Advances and General Trends.

Enhancement of axial magnetic anisotropy is the central objective to push forward the performance of Single-Molecule Magnet (SMM) complexes. In the case of mononuclear lanthanide complexes, the chemical environment around the paramagnetic ion must be tuned to place strongly interacting ligands along either the axial positions or the equatorial plane, depending on the oblate or prolate preference of the selected lanthanide. One classical strategy to achieve a precise chemical environment for a metal centre is using highly structured, chelating ligands. A natural approach for axial-equatorial control is the employment of macrocycles acting in a belt conformation, providing the equatorial coordination environment, and leaving room for axial ligands. In this review, we present a survey of SMMs based on the macrocycle belt motif. Literature systems are divided in three families (crown ether, Schiff-base and metallacrown) and their general properties in terms of structural stability and SMM performance are briefly discussed.

In Situ Synthesis of Fe3O4 Nanoparticles and Wood Composite Properties of Three Tropical Species.

Magnetic wood is a composite material that achieves harmony between both woody and magnetic functions through the active addition of magnetic characteristics to the wood itself. In addition to showing magnetic characteristics, magnetic wood offers low specific gravity, humidity control and acoustic absorption ability. It has potential for broad applications in the fields of electromagnetic wave absorption, electromagnetic interference shielding, furniture, etc. This work reports on the synthesis of Fe3O4 nanoparticles (NPs) in wood from three tropical species (Pinus oocarpa, Vochysia ferruginea and Vochysia guatemalensis) using a solution of iron (III) hexahydrate and iron (II) chloride tetrahydrate with a molar ratio of 1.6:1 at a concentration of 1.2 mol/L ferric chlorate under 700 kPa pressure for 2 h. Afterward, the wood samples were impregnated with an ammonia solution with three different immersion times. The treated wood (wood composites) was evaluated for the weight gain percentage (WPG), density, ash content and Fe3O4 content by the Fourier transform infrared spectroscopy (FTIR) spectrum, X-ray diffraction (XRD) and vibrating sample magnetometry (VSM). The results show that the species P. oocarpa had the lowest values of WPG, and its density decreased in relation to the untreated wood, with lower ash and Fe3O4 NP content. The XRD and some FTIR signals associated with changes in the wood component showed small differences from the untreated wood. Fe3O4 NPs presented nanoparticles with the smallest diameter of (approx. 7.3 to 8.5 nm), and its saturation magnetization (Ms) parameters were the lowest. On the other hand, V. guatemalensis was the species with the best Ms values, but the wood composite had the lowest density. In relation to the different immersion times, the magnetic properties were not statistically affected. Finally, the magnetization values of the studied species were lower than those of the pure Fe3O4 nanoparticles, since the species only have a certain amount of these nanoparticles (NPs), and this was reflected proportionally in the magnetization of saturation.

Structures of Dimer-of-Dimers Type Defect Cubane Tetranuclear Copper(II) Complexes with Novel Dinucleating Ligands.

Only a limited number of multinucleating ligands can stably maintain multinuclear metal structures in aqueous solutions. In this study, a water-soluble dinucleating ligand, 2,6-bis{[N-(carboxylatomethyl)-N-methyl-amino]methyl}-4-methylphenolate ((sym-cmp)3-), was prepared and its copper(II) complexes were structurally characterized. Using the single-crystal X-ray diffraction method, their dimer-of-dimers type defect cubane tetranuclear copper(II) structures were characterized for [Cu4(sym-cmp)2Cl2(H2O)2] and [Cu4(sym-cmp)2(CH3O)2(CH3OH)2]. In the complexes, each copper(II) ion has a five-coordinate square-pyramidal coordination geometry. The coordination bond character was confirmed by the density functional theory (DFT) calculation on the basis of the crystal structure, whereby we found the bonding and anti-bonding molecular orbitals. From the cryomagnetic measurement and the magnetic analysis, overall antiferromagnetic interaction was observed, and this magnetic behavior is also explained by the DFT result. Judging from the molar conductance and the electronic spectra, the bridging chlorido ligand dissociates in water, but the dinuclear copper(II) structure was found to be maintained in an aqueous solution. In conclusion, the tetranuclear copper(II) structures were crystallographically characterized, and the dinuclear copper(II) structures were found to be stabilized even in an aqueous solution.

Mechanochemical Synthesis and Nitrogenation of the Nd1.1Fe10CoTi Alloy for Permanent Magnet.

In this work, the mechanochemical synthesis method was used for the first time to produce powders of the nanocrystalline Nd1.1Fe10CoTi compound from Nd2O3, Fe2O3, Co and TiO2. High-energy-milled powders were heat treated at 1000 °C for 10 min to obtain the ThMn12-type structure. Volume fraction of the 1:12 phase was found to be as high as 95.7% with 4.3% of a bcc phase also present. The nitrogenation process of the sample was carried out at 350 °C during 3, 6, 9 and 12 h using a static pressure of 80 kPa of N2. The magnetic properties Mr, µ0Hc, and (BH)max were enhanced after nitrogenation, despite finding some residual nitrogen-free 1:12 phase. The magnetic values of a nitrogenated sample after 3 h were Mr = 75 Am2 kg-1, µ0Hc = 0.500 T and (BH)max = 58 kJ·m-3. Samples were aligned under an applied field of 2 T after washing and were measured in a direction parallel to the applied field. The best value of (BH)max ~ 114 kJ·m-3 was obtained for 3 h and the highest µ0Hc = 0.518 T for 6 h nitrogenation. SEM characterization revealed that the particles have a mean particle size around 360 nm and a rounded shape.

Study of the Influence of Magnetite Nanoparticles Supported on Thermally Reduced Graphene Oxide as Filler on the Mechanical and Magnetic Properties of Polypropylene and Polylactic Acid Nanocomposites.

A study addressed to develop new recyclable and/or biodegradable magnetic polymeric materials is reported. The selected matrices were polypropylene (PP) and poly (lactic acid) (PLA). As known, PP corresponds to a non-polar homo-chain polymer and a commodity, while PLA is a biodegradable polar hetero-chain polymer. To obtain the magnetic nanocomposites, magnetite supported on thermally reduced graphene oxide (TrGO:Fe3O4 nanomaterial) to these polymer matrices was added. The TrGO:Fe3O4 nanomaterials were obtained by a co-precipitation method using two types of TrGO obtained by the reduction at 600 °C and 1000 °C of graphite oxide. Two ratios of 2.5:1 and 9.6:1 of the magnetite precursor (FeCl3) and TrGO were used to produce these nanomaterials. Consequently, four types of nanomaterials were obtained and characterized. Nanocomposites were obtained using these nanomaterials as filler by melt mixer method in polypropylene (PP) or polylactic acid (PLA) matrix, the filler contents were 3, 5, and 7 wt.%. Results showed that TrGO600-based nanomaterials presented higher coercivity (Hc = 8.5 Oe) at 9.6:1 ratio than TrGO1000-based nanomaterials (Hc = 4.2 Oe). PLA and PP nanocomposites containing 7 wt.% of filler presented coercivity of 3.7 and 5.3 Oe, respectively. Theoretical models were used to analyze some relevant experimental results of the nanocomposites such as mechanical and magnetic properties.

Modeling the aluminum-doped and single vacancy blue phosphorene interactions with molecules: a density functional theory study.

Structural, electronic, binding energies and magnetic properties of aluminum-doped and single vacancy blue phosphorene interacting with pollutant molecules are investigated using the density functional theory (DFT) with periodic boundary conditions. Acetylene, ozone, sulfur trioxide, hydrogen selenide, and sulfur dichloride molecules are considered to show the efficiency and enhancement of the sensing properties in comparison with the pristine blue phosphorene. Acetylene, sulfur trioxide, hydrogen selenide, and sulfur dichloride show chemisorption (> 0.5 eV/molecule) when interacting with the aluminum-doped system, but the ozone molecule dissociates in all configurations and symmetry sites. On the other hand, the acetylene, ozone, and sulfur trioxide with the single vacancy blue phosphorene exhibit chemisorption, the hydrogen selenide molecule exhibit a weak interaction energy, and the sulfur dichloride dissociates in all configurations and symmetry sites. In all the cases, the enhancement in the interaction energy was achieved when compared to other results for the same molecules. Finally, the single vacancy blue phosphorene shows a magnetic moment of ~1 µB/supercell, as induced by the vacancy.

Chitosan-polyvinylpyrrolidone CoxFe3-xO4 (0.25 ≤ x ≤ 1) nanoparticles for hyperthermia applications.

Blends of chitosan (CS) and polyvinylpyrrolidone (PVP) with cobalt ferrite nanoparticles (CoFe2O4) have the potential for use in several biomedical applications as drug delivery systems and for hyperthermia applications. Herein, we present a detailed study of the effect of chitosan and PVP on the structural, magnetic and specific absorption rate (SAR) properties of CoxFe3-xO4 (x = 0.25, 0.50, 0.75 and 1.00) as an effective heat nanomediator for hyperthermia. Structural characterization was carried out using X-ray diffraction (XRD), infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Magnetic properties as a function of the Co2+ content were studied using a vibrating sample magnetometer (VSM) at room temperature. Hyperthermia investigations were performed at 454 ±â€¯20 kHz with a magnetic field amplitude of 5.5 mT. CS-PVP coated nanoparticles at x = 1.00 show a maximum SAR of 386 W/g, while bare nanoparticles show a SAR of 270 W/g. The advantage of the designed nanoparticles coated system lies in the fact that the versatile blending of chitosan and PVP enhance the SAR properties for hyperthermia of cobalt ferrite nanoparticles and provide biocompatibility and stability to the samples.

An Oxalate-Bridged Copper(II) Complex Combining Monodentate Benzoate, 2,2'-bipyridine and Aqua Ligands: Synthesis, Crystal Structure and Investigation of Magnetic Properties.

A dinuclear copper(II) complex of formula [{Cu(bipy)(bzt)(OH2)}2(µ-ox)] (1) (where bipy = 2,2'-bipyridine, bzt = benzoate and ox = oxalate) was synthesised and characterised by diffractometric (powder and single-crystal XRD) and thermogravimetric (TG/DTG) analyses, spectroscopic techniques (IR, Raman, electron paramagnetic resonance spectroscopy (EPR) and electronic spectroscopy), magnetic measurements and density functional theory (DFT) calculations. The analysis of the crystal structure revealed that the oxalate ligand is in bis(bidentate) coordination mode between two copper(II) centres. The other four positions of the coordination environment of the copper(II) ion are occupied by one water molecule, a bidentate bipy and a monodentate bzt ligand. An inversion centre located on the ox ligand generates the other half of the dinuclear complex. Intermolecular hydrogen bonds and π-π interactions are responsible for the organisation of the molecules in the solid state. Molar magnetic susceptibility and field dependence magnetisation studies evidenced a weak intramolecular-ferromagnetic interaction (J = +2.9 cm-1) between the metal ions. The sign and magnitude of the calculated J value by density functional theory (DFT) are in agreement with the experimental data.