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Two heterometallic Cu(II)/Ni(II) coordination polymers, [Cu2(Hbdea)2Ni(CN)4]n (1) and [Cu2(dmea)2Ni(CN)4]n·nH2O (2), were successfully self-assembled in water by reacting Cu(II) nitrate with H2bdea (N-butyldiethanolamine) and Hdmea (N,N-dimethylethanolamine) in the presence of sodium hydroxide and [Ni(CN)4]2-. These new coordination polymers were investigated by single-crystal and powder X-ray diffraction and fully characterized by FT-IR spectroscopy, thermogravimetry, elemental analysis, variable-temperature magnetic susceptibility measurements, and theoretical DFT and CASSCF calculations. Despite differences in crystal systems, in both compounds, each dinuclear building block [Cu2(µ-aminopolyalcoholate)2]2+ is bridged by diamagnetic [Ni(CN)4]2- linkers, resulting in 1D (1) or 2D (2) metal-organic architectures. Experimental magnetic studies show that both compounds display strong antiferromagnetic coupling (J = -602.1 cm-1 for 1 and -151 cm-1 for 2) between Cu(II) ions within the dimers mediated by the µ-O-alkoxo bridges. These results are corroborated by the broken symmetry DFT studies, which also provide further insight into the electronic structures of copper dimeric units. By reporting a facile self-assembly synthetic protocol, this study can be a model to widen a still limited family of heterometallic Cu/Ni coordination polymer materials with different functional properties.
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This study aimed to develop multifunctional nanoplatforms for both cancer imaging and therapy using superparamagnetic iron oxide nanoparticles (SPIONs). Two distinct synthetic methods, reduction-precipitation (MR/P) and co-precipitation at controlled pH (MpH), were explored, including the assessment of the coating's influence, namely dextran and gold, on their magnetic properties. These SPIONs were further functionalized with gadolinium to act as dual T1/T2 contrast agents for magnetic resonance imaging (MRI). Parameters such as size, stability, morphology, and magnetic behavior were evaluated by a detailed characterization analysis. To assess their efficacy in imaging and therapy, relaxivity and hyperthermia experiments were performed, respectively. The results revealed that both synthetic methods lead to SPIONs with similar average size, 9 nm. Mössbauer spectroscopy indicated that samples obtained from MR/P consist of approximately 11-13% of Fe present in magnetite, while samples obtained from MpH have higher contents of 33-45%. Despite coating and functionalization, all samples exhibited superparamagnetic behavior at room temperature. Hyperthermia experiments showed increased SAR values with higher magnetic field intensity and frequency. Moreover, the relaxivity studies suggested potential dual T1/T2 contrast agent capabilities for the coated SPpH-Dx-Au-Gd sample, thus demonstrating its potential in cancer diagnosis.
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Medios de Contraste , Nanopartículas Magnéticas de Óxido de Hierro , Imagen por Resonancia Magnética , Nanopartículas de Magnetita , Nanomedicina Teranóstica , Nanopartículas Magnéticas de Óxido de Hierro/química , Imagen por Resonancia Magnética/métodos , Medios de Contraste/química , Nanopartículas de Magnetita/química , Nanopartículas de Magnetita/uso terapéutico , Humanos , Oro/química , Dextranos/química , Gadolinio/química , Propiedades de Superficie , Hipertermia Inducida/métodos , Tamaño de la PartículaRESUMEN
Three mixed-valence barium iron fluorides, Ba7Fe7F34, Ba2Fe2F9, and BaFe2F7, were prepared through hydrothermal redox reactions. The characteristic structures of these compounds feature diverse distributions of FeIIF6 octahedra and FeIIIF6 groups. Ba7Fe7F34 contained one-dimensional infinite ∞[FeIIFeIII6F34]14- double chains, comprising cis corner-sharing octahedra along the b direction; Ba2Fe2F9 contained one-dimensional ∞[Fe2F9]4- double chains, consisting of cis corner-sharing octahedra along the chain (a-axis direction) and trans corner-sharing octahedra vertical to the chain, while BaFe2F7 revealed three-dimensional (3D) frameworks that consist of isolated edge-sharing dinuclear FeII2F10 units linked via corners by FeIIIF6 octahedra. Magnetization and Mössbauer spectroscopy measurements revealed that Ba7Fe7F34 exhibits an antiferromagnetic phase transition at â¼11 K, where ferrimagnetic ∞[FeIIFeIII6F34]14- double chains are arranged in a paralleling manner, while Ba2Fe2F9 shows canted antiferromagnetic ordering at â¼32.5 K, leading to noncollinear spin ordering.
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The complete structure revision of the RE2PdGe3 (RE = rare-earth metal) series revealed that Yb2PdGe3 is the only AlB2 ordered superstructure. Good-quality single crystals of this compound were successfully grown from molten indium flux, enabling accurate single-crystal investigations. Yb2PdGe3 crystallizes with the Ce2CoSi3-type structure in the hexagonal space group P6/mmm (no. 191) with lattice parameters a = 8.468(1) Å and c = 4.0747(7) Å. This structure is a four-order derivative of AlB2, composed of planar ∞2[PdGe3] honeycomb layers spaced by Yb species, located at the center of Ge6 and Ge4Pd2 hexagons. A superconducting transition is observed below the critical temperature of 4 K. A divalent state of Yb is deduced from magnetic susceptibility measurements below room temperature, which indicate an almost nonmagnetic behavior. A charge transfer from Yb to Pd and Ge was evidenced by the Quantum Theory of Atoms in Molecules (QTAIM) effective charges; polar four-atomic Ge-Pd/Yb and two-atomic Pd-Yb bonds were observed from the ELI-D (electron localizability indicator), partial ELI-D, and ELI-D/QTAIM intersections. The bonding interactions between Ge atoms within regular Ge6 hexagons are found to be intermediate between single bonds, as in elemental Ge, and higher-order bonds in the hypothetic Ge6H6 and Ge66- aromatic molecules.
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A new homoleptic Co(II) complex bearing two highly sterically congested 2-formiminopyrrolyl N,N'-chelating ligands is reported, displaying slow relaxation of the magnetisation at zero static (DC) field. This compound shows a large value for the zero-field splitting (ZFS) parameter D of -42.6(4) cm-1 leading to a spin-reversal energy barrier Ueff of 85 cm-1.
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Inorganic glass is a transparent functional material and one of the few materials that keeps leading innovation. In the last decades, inorganic glass was integrated into opto-electronic devices such as optical fibers, semiconductors, solar cells, transparent photovoltaic devices, or photonic crystals and in smart materials applications such as environmental, pharmaceutical, and medical sensors, reinforcing its influence as an essential material and providing potential growth opportunities for the market. Moreover, inorganic glass is the only material that is 100% recyclable and can incorporate other industrial offscourings and/or residues to be used as raw materials. Over time, inorganic glass experienced an extensive range of fabrication techniques, from traditional melting-quenching (with an immense diversity of protocols) to chemical vapor deposition (CVD), physical vapor deposition (PVD), and wet chemistry routes as sol-gel and solvothermal processes. Additive manufacturing (AM) was recently added to the list. Bulks (3D), thin/thick films (2D), flexible glass (2D), powders (2D), fibers (1D), and nanoparticles (NPs) (0D) are examples of possible inorganic glass architectures able to integrate smart materials and opto-electronic devices, leading to added-value products in a wide range of markets. In this review, selected examples of inorganic glasses in areas such as: (i) magnetic glass materials, (ii) solar cells and transparent photovoltaic devices, (iii) photonic crystal, and (iv) smart materials are presented and discussed.
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Polymeric platforms obtained by three-dimensional (3D) printing are becoming increasingly important as multifunctional therapeutic systems for bone treatment applications. In particularly, researchers aim to control bacterial biofilm on these 3D-platforms and enhance re-growing bone tissue, at the same time. This study aimed to fabricate a 3D-printed polylactic acid platform loaded with hydroxyapatite (HA), iron oxide nanoparticles (IONPs) and an antibiotic (minocycline) with tuneable properties and multistimuli response. IONPs were produced by a facile chemical co-precipitation method showing an average diameter between 11 and 15 nm and a superparamagnetic behaviour which was preserved when loaded into the 3D-platforms. The presence of two types of nanoparticles (IONPs and HA) modify the nanomorphological/nanotopographical feature of the 3D-platforms justifying their adequate bioactivity profile and in vitro cellular effects on immortalized and primary osteoblasts, including cytocompatibility and increased osteogenesis-related gene expression (RUNX2, BGLAP and SPP1). Disk diffusion assays and SEM analysis confirmed the effect of the 3D-platforms loaded with minocycline against Staphylococcus aureus. Altogether results showed that fabricated 3D-platforms combined the exact therapeutic antibiofilm dose of the antibiotic against S. aureus, with the enhanced osteogenic stimulation of the HA and IONPs nanoparticles which is a disruptive approach for bone targeting applications.
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Nanopartículas de Magnetita , Nanopartículas , Antibacterianos/farmacología , Regeneración Ósea , Huesos , Osteogénesis , Impresión Tridimensional , Staphylococcus aureus , Andamios del TejidoRESUMEN
Tetraphenylphosphonium salts of Co and Fe complexes with alkyl-substituted, tert-butyl (tb), and isopropyl (dp) 2,3-thiophenedithiolate (α-tpdt) ligands, namely, TPP[Co(α-tb-tpdt)2] (3), TPP2[Fe(α-tb-tpdt)2]2 (4a-b), TPP[Co(α-dp-tpdt)2] (5), and TPP[Fe(α-dp-tpdt)2] (6) were prepared and characterized by cyclic voltammetry, single crystal X-ray diffraction, magnetic susceptibility measurements, and 57Fe Mössbauer spectroscopy. Compound 3 and 5 are isostructural with their Au and Ni analogues with a square-planar coordination geometry. Compound 4 presents two polymorphs (4a-b) both showing a Fe(III) bisdithiolene dimerization. The magnetic susceptibility of 3 and 5 exhibits behavior dominated by antiferromagnetic interactions, with room-temperature magnetic moments of 3.40 and 3.36 µB, respectively, indicating that these square-planar Co(III) complexes assume an intermediate spin electronic configuration (S = 1) as supported by multiconfigurational and DFT calculations.
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Superparamagnetic iron oxide nanoparticles (SPIONs) have shown great potential in biomedicine due to their high intrinsic magnetization behaviour. These are small particles of magnetite or maghemite, and when coated, their surface oxidation is prevented, their aggregation tendency is reduced, their dispersity is improved, and the stability and blood circulation time are increased, which are mandatory requirements in biomedical applications. In this work, SPIONs were synthesized in air through a reduction-precipitation method and coated with four different polymers (Polyethylene glycol(PEG) 1000/6000 and dextran T10/T70). All the synthesized samples were structurally and magnetically characterized by transmission electron microscopy, Fourier transform infra-red spectroscopy, X-ray powder diffraction, Mössbauer spectroscopy, and Superconducting Quantum Interference Device (SQUID) magnetometry. SPIONs centrifuged and dried in vacuum with an average diameter of at least 7.5 nm and a composition ≤60% of maghemite and ≥40% of magnetite showed the best magnetization results, namely a saturation magnetization of ~64 emu/g at 300 K, similar to the best reported values for SPIONs prepared in controlled atmosphere. As far as SPIONs' coatings are concerned, during their preparation procedure, surface polymers must be introduced after the SPIONs' precipitation. Furthermore, polymers with shorter chains do not affect the SPIONs' magnetization performance, although longer chain polymers significantly decrease the coated particle magnetization values, which is undesirable.
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Early actinide ions have large spin-orbit couplings and crystal field interactions, leading to large anisotropies. The success in using actinides as single-molecule magnets has so far been modest, underlining the need for rational strategies. Indeed, the electronic structure of actinide single-molecule magnets and its relation to their magnetic properties remains largely unexplored. A uranium(III) single-molecule magnet, [UIII {SiMe2 NPh}3 -tacn)(OPPh3 )] (tacn=1,4,7-triazacyclononane), has been investigated by means of a combination of magnetic, spectroscopic and theoretical methods to elucidate the origin of its static and dynamic magnetic properties.
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Three layered lanthanide hydroxides (LLHs), with the general formula Ln8(OH)20Cl4·nH2O (Ln = Tb (1), Ho (2), Er (3)), were prepared and magnetically characterized both as pure compounds and diluted within a yttrium diamagnetic matrix, LYH : xLn, LYH : 0.044Tb (1'), LYH : 0.045Ho (2'), and LYH : 0.065Er (3'). This study was complemented with theoretical calculations in order to understand the electronic configuration and the contributions to the slow relaxation behavior. In the pure compounds dominant 3D ferromagnetic interactions are observed, with a small magnetization hysteresis at 1.8 K for 1, while the magnetically diluted solid solutions display slow relaxation of magnetization at low temperatures.
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The 5-substituted 2-aryliminopyrrolyl ligand precursors of the type 5-R-2-[ N-(2,6-diisopropylphenyl)formimino]-1 H-pyrrole (R = 2,6-Me2-C6H3 (1a), 2,4,6-iPr3-C6H2 (1b), 2,4,6-Ph3-C6H3 (1c; reported in this work), anthracen-9-yl (1d), CPh3 (1e; reported in this work)) were treated with K[N(SiMe3)2] in toluene to yield the respective 5-R-2-[ N-(2,6-diisopropylphenyl)formimino]pyrrolyl potassium salts 2a-e in high yields. The paramagnetic 15-electron Co(II) complexes of the type [Co{κ2 N,N'-5-R-NC4H2-2-C(H)âN(2,6-iPr2-C6H3)}(Py)Cl] (3a-e; Py = pyridine) were prepared by salt metathesis of CoCl2(Py)4 with the respective potassium salts 2a-e in moderate to good yields. When the CoCl2(THF)1.5 precursor was combined with the in situ prepared sodium salt of ligand precursor 1b, the trinuclear complex [Co{κ2 N, N'-5-(2,4,6-iPr3-C6H2)-NC4H2-2-C(H)âN(2,6-iPr2-C6H3)}(µ-Cl)]2[(µ-Cl)2Co(THF)2] (4) was obtained in high yields. Complexes 3a-e have high-spin electronic configurations both in solution and in the solid state. X-ray diffraction studies of complexes 3a,e confirmed distorted tetrahedral coordination geometries. Complex 4, on the other hand, is a linear trinuclear Co(II)-Co(II)-Co(II) complex with two terminal distorted tetrahedral four-coordinate sites and a central octahedral six-coordinate site, all in the high-spin state, S = 3/2, as confirmed by the magnetization measurements and DFT calculations. Solid-state magnetic measurements in both complexes 3a and 4 point to paramagnetic behavior with a significant contribution of spin-orbit coupling. Additionally, intramolecular antiferromagnetic coupling of the adjacent cobalt atoms is observed in 4. The Co(II) family 3a-d, on activation with K(HBEt3), catalyzed the hydroboration of several α-olefins with pinacolborane, in good to high yields (50-80%). This system almost exclusively yielded the anti-Markovnikov (a-Mk) addition product, except when styrene was used, where the selectivity in the Markovnikov (Mk) product increased with increasing steric bulkiness of the 5-R-2-iminopyrrolyl substituent, with the a-Mk:Mk molar ratio varying from 2.33:1 (3a, R = 2,6-Me2-C6H3) to 0.75:1 (3c, R = 2,4,6-Ph3-C6H3). Preliminary mechanistic studies indicate that the activation by K(HBEt3) gave rise to a Co(I) species, the catalyst system likely following an oxidative addition pathway.
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Gold and nickel bisdithiolene complexes with methyl and tert-butyl substituted thiophenetetrathiafulavalenedithiolate ligands (α-mtdt and α-tbtdt) were prepared and characterized. These complexes were obtained, under anaerobic conditions, as tetrabutylammonium salts. The diamagnetic gold monoanion (n-Bu4N)[Au(α-mtdt)2] (3) and nickel dianionic species (n-Bu4N)x[Ni(α-mtdt)2] (x = 1,2) (4) were similar to the related non-substituted extended thiophenic-TTF (TTF = tetrathiafulvalene) bisdithiolenes. However the introduction of the large, bulky substituent tert-butyl, led to the formation of a Au (I) dinuclear complex, (n-Bu4N)2[Au2(α-tbtdt)2] (5). The neutral methyl substituted gold and nickel complexes were easily obtained through air or iodine exposure as polycrystalline or amorphous fine powder. [Au(α-mtdt)2] (6) and [Ni(α-mtdt)2] (7) polycrystalline samples display properties of a metallic system with a room temperature electrical conductivity of 0.32 S/cm and ≈4 S/cm and a thermoelectric power of ≈5 µV/K and ≈32 µV/K, respectively. While [Au(α-mtdt)2] (6) presented a Pauli-like magnetic susceptibility typical of conducting systems, in [Ni(α-mtdt)2] (7) large magnetic susceptibilities indicative of high spin states were observed. Both electric transport properties and magnetic properties for gold and nickel [M(α-mtdt)2] are indicative that these compounds are single component molecular conductors.
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Complejos de Coordinación/química , Oro/química , Níquel/química , Tiofenos/química , Cristalografía por Rayos X , Ligandos , Modelos Moleculares , Compuestos Organometálicos/químicaRESUMEN
The crystal structure of (µ3-oxo)hexakis(cyanoacetato-κO,O')(cyanoacetato-κO)diaquatriiron(III) cyanoacetic acid shows the formation of trinuclear complexes in a hydrogen-bond network that bonds all the molecules in a 3D arrangement. For this complex, within whose clusters the whole magnetic interaction takes place, 57Fe Mössbauer spectroscopy shows that the Fe cations are in the S=5/2 state in the temperature range 2-295K. The asymmetric broadening of the absorption peaks below 80K is consistent with strong antiferromagnetic interactions between the metal spins. The magnetization measurements also show the antiferromagnetic character of the spin ensemble and an ST=1/2 magnetic ground state typical of triangular systems with similar J between Fe-Fe pairs.
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Chitosan is a biopolymer widely used for biomedical applications such as drug delivery systems, wound healing, and tissue engineering. Chitosan can be used as coating for other types of materials such as iron oxide nanoparticles, improving its biocompatibility while extending its range of applications. In this work iron oxide nanoparticles (Fe3O4 NPs) produced by chemical precipitation and thermal decomposition and coated with chitosan with different molecular weights were studied. Basic characterization on bare and chitosan-Fe3O4 NPs was performed demonstrating that chitosan does not affect the crystallinity, chemical composition, and superparamagnetic properties of the Fe3O4 NPs, and also the incorporation of Fe3O4 NPs into chitosan nanoparticles increases the later hydrodynamic diameter without compromising its physical and chemical properties. The nano-composite was tested for magnetic hyperthermia by applying an alternating current magnetic field to the samples demonstrating that the heating ability of the Fe3O4 NPs was not significantly affected by chitosan.
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Quitosano/química , Fenómenos Magnéticos , Nanopartículas de Magnetita/química , Temperatura , Peso MolecularRESUMEN
A tetravalent uranium compound with a radical azobenzene ligand, namely, [{(SiMe2 NPh)3 -tacn}U(IV) (η(2) -N2 Ph2 (.) )] (2), was obtained by one-electron reduction of azobenzene by the trivalent uranium compound [U(III) {(SiMe2 NPh)3 -tacn}] (1). Compound 2 was characterized by single-crystal X-ray diffraction and (1) Hâ NMR, IR, and UV/Vis/NIR spectroscopy. The magnetic properties of 2 and precursor 1 were studied by static magnetization and ac susceptibility measurements, which for the former revealed single-molecule magnet behaviour for the first time in a mononuclear U(IV) compound, whereas trivalent uranium compound 1 does not exhibit slow relaxation of the magnetization at low temperatures. A first approximation to the magnetic behaviour of these compounds was attempted by combining an effective electrostatic model with a phenomenological approach using the full single-ion Hamiltonian.
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Iron oxide nanoparticles (NPs) have been extensively studied in the last few decades for several biomedical applications such as magnetic resonance imaging, magnetic drug delivery and hyperthermia. Hyperthermia is a technique used for cancer treatment which consists in inducing a temperature of about 41-45 °C in cancerous cells through magnetic NPs and an external magnetic field. Chemical precipitation was used to produce iron oxide NPs 9 nm in size coated with oleic acid and trisodium citrate. The influence of both stabilizers on the heating ability and in vitro cytotoxicity of the produced iron oxide NPs was assessed. Physicochemical characterization of the samples confirmed that the used surfactants do not change the particles' average size and that the presence of the surfactants has a strong effect on both the magnetic properties and the heating ability. The heating ability of Fe3O4 NPs shows a proportional increase with the increase of iron concentration, although when coated with trisodium citrate or oleic acid the heating ability decreases. Cytotoxicity assays demonstrated that both pristine and trisodium citrate Fe3O4 samples do not reduce cell viability. However, oleic acid Fe3O4 strongly reduces cell viability, more drastically in the SaOs-2 cell line. The produced iron oxide NPs are suitable for cancer hyperthermia treatment and the use of a surfactant brings great advantages concerning the dispersion of NPs, also allowing better control of the hyperthermia temperature.
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Coloides/química , Nanopartículas de Magnetita/química , Tensoactivos/química , Animales , Supervivencia Celular/efectos de los fármacos , Chlorocebus aethiops , Coloides/toxicidad , Calor , Nanopartículas de Magnetita/toxicidad , Células VeroRESUMEN
(α-DT-TTF)2[Au(i-mnt)2] and (α-DT-TTF)2[Co(mnt)2] are two new salts of the donor α-dithiophene-tetrathiafulvalene with stable diamagnetic anions, both presenting a ladder structure of the donors organized in paired segregated stacks. The first one is isostructural with previously reported closely related compounds and presents a magnetic spin-ladder behavior with Jâ¥= 83.5 K and J⥠= 110.3 K as estimated from spin susceptibility data in single crystals. (α-DT-TTF)2[Co(mnt)2] presents a new structural type with a different arrangement of pairs of donor stacks, alternating with stacks of dimerized [Co(mnt)2] anions which are however arranged in an uncorrelated fashion perpendicular to the stacking axis. Due to the strong coupling between the disordered anion chains and the donor chains, this compound does not present a magnetic spin-ladder behavior. The low temperature superstructure of (DT-TTF)2[Cu(mnt)2] below the transition at 235 K, previously known to be associated with a lattice doubling along the stacking axis, was solved by synchrotron radiation diffraction in small single crystals. It is found that this dimerization is due to donor charge localization with the spin carriers being associated with fully oxidized donor species alternating with neutral donors.
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The magnetic properties of layered dysprosium hydroxides, both diluted in the diamagnetic yttrium analogous matrix (LYH:0.04Dy), and intercalated with 2,6-naphthalene dicarboxylate anions (LDyH-2,6-NDC), were studied and compared with the recently reported undiluted compound (LDyH = Dy8(OH)20Cl4·6H2O). The Y diluted compound reveals a single-molecule magnet (SMM) behavior of single Dy ions, with two distinct slow relaxation processes of the magnetization at low temperatures associated with the two main types of Dy sites, 8- and 9-fold coordinated. Only one relaxation process is observed in both undiluted LDyH and intercalated compounds as a consequence of dominant ferromagnetic Dy-Dy interactions, both intra- and interlayer. Semiempirical calculations using a radial effect charge (REC) model for the crystal field splitting of the Dy levels are used to explain data in terms of contributions from the different Dy sites. The dominant ferromagnetic interactions are explained in terms of orientations of easy magnetization axes obtained by REC calculations together with the sign of the superexchange expected from the Dy-O-Dy angles.
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The Fe(III) complexes Fe(5-Br-qsal)2Ni(dmit)2·solv with solv = CH2Cl2 (1) and (CH3)2CO (2) were synthesized, and their structural and magnetic properties were studied. While magnetization and Mössbauer spectroscopy data of 1 showed a gradual spin transition, compound 2 evidenced an abrupt transition with a thermal hysteresis of 13 K close to room temperature (T1/2 ↓ â¼273 K and T1/2 ↑ â¼286 K). A similar packing arrangement of segregated layers of cations and anions was found for 1 and 2. In both low-spin, LS, structures there are a large number of short intra- and interchain contacts. This number is lower in the high-spin, HS, phases, particularly in the case of 1. The significant loss of strong π-π interactions in the cationic chains and short contacts in the anionic chains in the HS structure of 1 leads to alternating strong and weak bonds between cations along the cationic chains and the formation of unconnected dimers along the anionic chains. This is consistent with a significant weakening of the extended interactions in 1. On the other hand, in the HS phase of 2 the 3D dimensionality of the short contacts observed in the LS phases is preserved. The effect of distinct solvent molecules on the intermolecular spacings explains the different spin crossover behaviors of the title compounds.