Variable-temperature Magnetization Research Articles

Axial Zero Thermal Expansion with Good Mechanical Strength in the Ni-Doped Kagome Ho2Fe17 Magnets.

Zero thermal expansion (ZTE) metals have drawn considerable scientific and practical interest due to their excellent dimensional stability. However, the narrow temperature window and inherent brittleness of the ZTE compounds severely limit their processing and application. Herein, an axial ZTE alloy (Ho2Fe13.8Ni3.2, αl = -0.3 × 10-6 K-1 and 110-545 K) is realized in the Ni-doped Ho2Fe17 magnets, which effectively broadens the ZTE temperature window. Combining the variable-temperature neutron diffraction and magnetization measurements, we reveal that the content of Ni tailors the ferromagnetic ordering of the Fe sublattice and regulates lattice negative thermal expansion. Good compressive strength is subsequently achieved by introducing excess Fe in the axial ZTE composition, namely, the dual-phase alloy of Ho2Fe13.8Ni3.2-Fe5 (αl = +0.3 × 10-6 K-1, 110-535 K, and 1.19 ± 0.2 GPa). Neutron diffraction and scanning electron microscopy reveal that the α phase (Fe-Ni) precipitates in the hexagonal phase matrix play a critical role in maintaining ZTE characteristics and enhancing compressive strength. The present chemical design approach may be applicable for obtaining high-performance axial ZTE alloys.

Synthesis, general physicochemical behaviour and magnetic studies of the macrocyclic bis-pyridine derivatives [TTDPzM(py)2]·2H2O (M = MnII, CoII, NiII)

In our extensive work on phthalocyanine-like macrocycles carrying peripherally attached strongly electron-withdrawing 1,2,5-thia/selenodiazol rings we recently reported on the FeII species of formula [TTDPzFe(py)2].2H2O (TTDPz = tetrakis(thiadiazole)porphyrazinato dianion). The present work deals with the synthesis and extended physicochemical studies of the series of related macrocycles [TTDPzM(py)2].2H2O (M = MnII, CoII, NiII). The diffractograms of three solid samples of the NiII complex [TTDPzNi(py)2]·2H2O, obtained from different synthetic procedures, indicate that the species is reproducibly obtained. All three samples are isomorphous with each other as shown by their X-ray powder diffractograms. Based on the comparison of the IR spectra of [TTDPzNi(py)2].2H2O and the related desolvated [TTDPzNi], the IR absorption peaks belonging to the pyridine molecules could be identified. The systematic presence of the two water molecules in all three species suggests that forms of contact do exist in the form of hydrogen bonds between them and the S and N atoms present peripherally in the thiadiazole groups of the macrocyclic units. As regard to the elimination of water, the thermograms (in inert atmosphere in the range 25–600 °C) indicate in all cases that loss of water occurs below 100 °C but loss of pyridine occurs over a broad range 100–300 °C for the MnII and CoII species whereas for the NiII complex it takes place in the narrow range 200–220 °C. In relation to the parallel series of metallophthalocyanines, i.e. [PcM] (M = MnII, FeII, CoII), it is noted that the NiII analog has not been reported in the literature and in a direct experiment it has been proved that [PcNi] heated in pyridine is obtained unchanged, the different behavior for the NiII TTDPz derivative due to the electron withdrawing effect of the external thiadiazole substituents, which makes favorable axial pyridine coordination in the complex. Completely insoluble in water, the triad of TTDPz derivatives is extremely low-soluble in non-donor or low donor solvents. This precluded any attempt to isolate single crystals for single-crystal X-ray work. Their UV–visible spectra show essential similarities in whatever organic solvent is used with clearly positioned Soret (300–400 nm) and Q-band absorptions (630–650 nm). Variable temperature magnetic susceptibility and magnetization studies reveal that the [TTDPzM(py)2].2H2O complexes all show paramagnetism with ground state spins of 3/2 (MnII), ½ (CoII) and 1 (NiII), supported by fitting the data to spin Hamiltonian formalism, vide infra. Comparisons are made with the magnetism of [PcM] analogues with key differences noted for M = NiII.

{Fe3} to {Fe6} clusters through changing flexible 1,3-propanediol to rigid ethylene glycol: Syntheses, structures and magnetic properties

Two related FeIII complexes [Fe3(μ3O)(O2CPh)6(H2L1)2(H2O)](NO3)·2C3H8O2 (1 {Fe3}) and [Fe6(μ3O)2(O2CPh)6(HL2)6](NO3)2·2CH3CN (2 {Fe6}) (H2L1 = 1,3-propanediol and H2L2 = ethylene glycol) were synthesized and characterized. Complex 1 consists of a [Fe3O(PhCO2)3] unit. Changing ethylene glycol to 1,3-propanediol, the final cluster 2 comprises two [Fe3O(PhCO2)3] triangular units connected by six mono-deprotonated µ2–1η:2η ethylene glycol. The result indicates that the syntheses of FeIII complexes is sensitive to the ligands. Variable-temperature (T) and field (B) solid-state direct current magnetization (M) studies show that complexes 1 and 2 show strong anti-ferromagnetic coupling between FeIII ions, resulting in ground-state spins of S = 1/2 for 1 and S = 0 for 2, which is also confirmed by the calculations.

Determining the Effects of Zero-Field Splitting and Magnetic Exchange in Dimeric Europium(II) Complexes.

Related BAP [BAP = bis(acyl)phosphide] and Acac (Acac = β-diketonate) molecules perform as robust supports for both lanthanide and actinide metals. Here, a molecular bimetallic Eu2+ complex was successfully targeted and isolated by employing sodium bis(mesitoyl)phosphide [Na(mesBAP)] in a salt metathesis with EuI2, producing [Eu(mesBAP)2(et2o)]2 (et2o = metal-coordinated diethyl ether). The corresponding Acac-Eu2+ complex was targeted using mesAcac- (1,3-dimesityl-1,3-propanedione), generating [Eu(mesAcac)2(et2o)]2. Both complexes were characterized by single-crystal X-ray diffraction, UV-vis, IR, and NMR spectroscopies, and variable-temperature magnetic susceptibility. [Eu(mesBAP)2(et2o)]2 was persistent under anaerobic, anhydrous conditions, whereas the analogous [Eu(mesAcac)2(et2o)]2 showed evidence of decomposition under identical conditions. Variable-temperature magnetic susceptibility and magnetization studies of [Eu(mesBAP)2(et2o)]2 and [Eu(mesAcac)2(et2o)]2 were performed, resulting in similar magnetic exchange coupling values of Jex = -0.018 and -0.023 cm-1 and axial zero-field-splitting D values of -0.38 and -0.51 cm-1, respectively.

Permanent Porosity in the Room-Temperature Magnet and Magnonic Material V(TCNE)2.

Materials that simultaneously exhibit permanent porosity and high-temperature magnetic order could lead to advances in fundamental physics and numerous emerging technologies. Herein, we show that the archetypal molecule-based magnet and magnonic material V(TCNE)2 (TCNE = tetracyanoethylene) can be desolvated to generate a room-temperature microporous magnet. The solution-phase reaction of V(CO)6 with TCNE yields V(TCNE)2·0.95CH2Cl2, for which a characteristic temperature of T* = 646 K is estimated from a Bloch fit to variable-temperature magnetization data. Removal of the solvent under reduced pressure affords the activated compound V(TCNE)2, which exhibits a T* value of 590 K and permanent microporosity (Langmuir surface area of 850 m2/g). The porous structure of V(TCNE)2 is accessible to the small gas molecules H2, N2, O2, CO2, ethane, and ethylene. While V(TCNE)2 exhibits thermally activated electron transfer with O2, all the other studied gases engage in physisorption. The T* value of V(TCNE)2 is slightly modulated upon adsorption of H2 (T* = 583 K) or CO2 (T* = 596 K), while it decreases more significantly upon ethylene insertion (T* = 459 K). These results provide an initial demonstration of microporosity in a room-temperature magnet and highlight the possibility of further incorporation of small-molecule guests, potentially even molecular qubits, toward future applications.

Coordination chemistry and magnetic properties of copper(II) halide complexes of quinoline

Complexes Cu(quin)2X2 [quin = quinoline, X = Cl (1), Br (2)] have been prepared and characterized via single-crystal X-ray diffraction and variable temperature magnetization measurements. The compounds are isomorphous in the monoclinic space group C2/c and crystallize as square planar complexes linked into chains via short X…X contacts. Magnetic susceptibility data were collected over the temperature range 1.8–300 K and were fitted to the one-dimensional Heisenberg antiferromagnetic model yielding J/kB = −33.7(5) K (1) and −145(4) K (2) with the larger exchange in the bromide complex a result of greater overlap due to the larger van der Waals contribution. Low temperature data indicate the presence of some short chains in the sample which provide for a paramagnetic contribution (odd length chains) or diamagnetic contribution (even length chains) at the lowest temperatures.

Transition metal halide complexes of 4′-aminoacetophenone: Syntheses, structures, and magnetic behavior

A family of eight compounds of the general formula [(C8H9NO)2MX2] or [(C8H9NO)2(H2O)2MX2], (M = Ni, Co, Cu, Zn; X = Cl, Br) has been prepared and the compounds characterized by combustion analysis, IR, single-crystal X-ray diffraction and variable temperature magnetization measurements. [[(C8H9NO)2(H2O)nMX2], (1, n = 0, M = Cu, X = Cl; 2, n = 0, M = Cu, X = Br; 3, n = 2, M = Ni, X = Cl; 4, n = 2, M = Ni, X = Br; 5, n = 2, M = Co, X = Cl; 6, n = 2, M = Co, X = Br; 7, n = 0, M = Zn, X = Cl; 8, n = 0, M = Zn, X = Br.) The eight compounds crystallize in three distinct space groups and have coordination number of either four (compounds 1, 2, 7, and 8) or six (compounds 3–6). Compounds 1 and 2 are slightly distorted square planar, compounds 3–6 are slightly distorted octahedral, and compounds 7 and 8 are slightly distorted tetrahedral. All eight compounds form chains either through bihalide interactions (1 and 2) or systems of hydrogen bonds (3–8). Chains are linked into layers through short halide…halide (1, 2, 7) and both traditional and non-traditional hydrogen bonds. The complexes have also been studied via variable temperature magnetic susceptibility measurements. Data for Cu(II) complexes 1 and 2 the 1D-Heisenberg uniform chain model with J/kB of −13.4(6) K and −14.3(4) K, respectively, with antiferromagnetic interchain interactions (θ = −4.1(5) K, −2.5(5) K, respectively) following the H=-J∑si∙sj Hamiltonian. The Ni(II) and Co(II) compounds showed temperature dependent moments which were well-modeled as arising due to single-ion anisotropy.

Exploration of Variable Temperature Magnetism and Electrical Properties of a Pyridyl-isonicotinoyl Hydrazone Bridged Three-Dimensional Mn-Metal–Organic Framework with a Thiophene Dicarboxylato Link

In emerging trends in our technology-dependent society, the applicability of multifunctional coordination polymers (CPs) and metal–organic frameworks is highly stimulating. In search of such chemical compounds, a Mn(II), d5, based metal–organic framework (MOF), {[Mn2(tdc)2(pcih)2(EtOH)]n} (1), has been designed with the coordination of multidentate ligands tdc2– (2,5-thiophene dicarboxylato) and pcih (pyridine-4-carboxaldehyde isonicotinoylhydrazone). The structure determination by single crystal X-ray diffraction has revealed the formation of three-dimensional (3D) supramolecular architecture via the combined nearly perpendicular bridging of pcih and tdc2– ligands. A variable temperature magnetic measurement of 1 shows weak antiferromagnetism (χMT, 9.41 cm3 K mol–1 at 300 K) with two as good as “isolated” Mn(II) centers (S = 5/2 with g ≈ 2.07). Magnetic exchange is considered through 9/10 carboxylato bridged atoms inclusively spanning two Mn(II) centers at a distance of 4.114 Å. Interestingly, the 3D assembly of 1 exhibits electrical conductivity in the semiconducting region (band gap, 3.72 eV; barrier height, 0.65 eV; series resistance, 0.03 Ω). A Schottky barrier diode feature is recorded at a threshold potential of 0.19 V and follows a non-ohmic relation (I α V2), and the conductivity is 3.42 × 10–5 S m–1. A galvanostatic charge–discharge (GCD) experiment measures the moderate specific capacitance of 1 F/g at a 2 mV/s scan rate.

Dinuclear Fluoride Single-Bridged Lanthanoid Complexes as Molecule Magnets: Unprecedented Coupling Constant in a Fluoride-Bridged Gadolinium Compound.

A new synthetic method allows isolating fluoride-bridged complexes Bu4N{[M(3NO2,5Br-H3L1,1,4)]2(μ-F)} (M = Dy, 1; M = Ho, 2; M = Gd, 3) and Bu4N{[Dy(3Br,5Cl-H3L1,2,4)]2(μ-F)}·2H2O, 4·2H2O. The crystal structures of 1·5CH3C6H5,·2·2H2O·0.75THF, 3, and 4·2H2O·2THF show that all of them are dinuclear compounds with linear single fluoride bridges and octacoordinated metal centers. Magnetic susceptibility measurements in the temperature range of 2–300 K reveal that the GdIII ions in 3 are weakly antiferromagnetically coupled, and this constitutes the first crystallographically and magnetically analyzed gadolinium complex with a fluoride bridge. Variable-temperature magnetization demonstrates a poor magnetocaloric effect for 3. Alternating current magnetic measurements for 1, 2, and 4·2H2O bring to light that 4·2H2O is an SMM, 1 shows an SMM-like behavior under a magnetic field of 600 Oe, while 2 does not show relaxation of the magnetization even under an applied magnetic field. In spite of this, 2 is the first fluoride-bridged holmium complex magnetically analyzed. DFT and ab initio calculations support the experimental magnetic results and show that apparently small structural differences between 1 and 4·2H2O introduce important changes in the dipolar interactions, from antiferromagnetic in 1 to ferromagnetic in 4·2H2O.

A New Class of Task-Specific Imidazolium Salts and Ionic Liquids and Their Corresponding Transition-Metal Complexes for Immobilization on Electrochemically Active Surfaces.

Adding to the versatile class of ionic liquids, we report the detailed structure and property analysis of a new class of asymmetrically substituted imidazolium salts, offering interesting thermal characteristics, such as liquid crystalline behavior, polymorphism or glass transitions. A scalable general synthetic procedure for N‐polyaryl‐N’‐alkyl‐functionalized imidazolium salts with para‐substituted linker (L) moieties at the aryl chain, namely [LPh m ImHR]+ (L=Br, CN, SMe, CO2Et, OH; m=2, 3; R=C12, PEG n ; n=2, 3, 4), was developed. These imidazolium salts were studied by single‐crystal X‐ray diffraction (SC‐XRD), NMR spectroscopy and thermochemical methods (DSC, TGA). Furthermore, these imidazolium salts were used as N‐heterocyclic carbene (NHC) ligand precursors for mononuclear, first‐row transition metal complexes (MnII, FeII, CoII, NiII, ZnII, CuI, AgI, AuI) and for the dinuclear Ti‐supported Fe‐NHC complex [(OPy)2Ti(OPh2ImC12)2(FeI2)] (OPy=pyridin‐2‐ylmethanolate). The complexes were studied concerning their structural and magnetic behavior via multi‐nuclear NMR spectroscopy, SC‐XRD analyses, variable temperature and field‐dependent (VT‐VF) SQUID magnetization methods, X‐band EPR spectroscopy and, where appropriate, zero‐field 57Fe Mössbauer spectroscopy.

Crystal structure, magnetic properties and luminescent behavior of four mononuclear lanthanide-radical complexes

Four mononuclear lanthanide complexes based on a long nitronly nitroxide radical NIT-PhOPyrim, [Ln(hfac)3(NIT-PhOPyrim)(H2O)] (Ln(Ⅲ) = Gd 1, Tb 2, Dy 3, Er4; hfac = hexafluoroacetylacetonate; NIT-PhOPyrim = 2-[4-(pyrimidin-2-yloxy)phenyl]-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide) have been synthesized and characterized. Single crystal X-ray diffraction analyses revealed that these four complexes are isomorphic in which each Ln(Ⅲ) ion is eight-coordinated by six oxygen atoms from three hfac ligands, one oxygen atom from one water molecule and one oxygen atom from the NO group of NIT-PhOPyrim ligand. Particularly, the coordinated water molecules were connected other mononuclear units through their hydrogen bonds into tetra-nuclear complexes and/or dimers. Variable temperature magnetization of complex 1 was shown the ferromagnetic interaction between Gd(III) ion and nitroxide radical, while weak intermolecular antiferromagnetic interactions through hydrogen bonds. Alternating-current (ac) magnetic susceptibility of complexes 2–4 revealed no magnetic relaxation behavior. Furthermore, Tb complex can detect Fe3+anion with a high sensitivity and selectivity through the fluorescence quenching effect.

Complex Featuring Two Double Dative Bonds Between Carbon(0) and Uranium

Complex Featuring Two Double Dative Bonds Between Carbon(0) and Uranium

Di-2-pyridyl ketone-based ligands as evergreen “trees” in the “forest” of manganese chemistry: Mononuclear Mn(III) complexes from the use of MnF3

The syntheses, crystal and electronic structures are reported of three new mononuclear Mn(III) complexes with the formulae [Mn{(py)2C(OMe)(O)}2(MeOH)2](PF6) (1), [Mn{(py)2C(OMe)(O)}2](PF6) (2) and [Mn{(py)2C(OMe)(O)}2](ClO4) (3), where (py)2C(OMe)(O)− is the monoanion of the hemiacetal form of di-2-pyridyl ketone, (py)2CO. They were obtained from the reactions of (py)2CO with MnF3 in the presence of (NH4)PF6 (1, 2) or NaClO4 (3) in refluxing MeOH. The complex cations are centrosymmetric pseudo-octahedral with a rhombic arrangement of the donor atoms; the anion (py)2C(OMe)(O)− behaves as a N,O-bidentate chelating (η1:η1) ligand in 1 and as a N,O,N-tridentate chelating (η1:η1:η1) ligand in 2 and 3. The 3D architectures of 1–3 are characterized by hydrogen-bonded chains of the cations surrounded by columns of the counterions and are formed through an extensive network of cation–anion hydrogen bonds. The three compounds are the first structurally characterized Mn(III) complexes with (py)2CO-based ligation. Variable-temperature magnetic susceptibility, magnetization isotherms and X-band EPR spectra of 1 and 2 reveal high-spin MnIII atoms (S = 2), anisotropy effects and a positive value of ~ +4 cm−1 of the zero--field splitting parameter D; moreover, EPR spectroscopy indicates the contribution of rhombic and/or higher order terms.

Anomalous magnetism of uranium(IV)-oxo and -imido complexes reveals unusual doubly degenerate electronic ground states

Anomalous magnetism of uranium(IV)-oxo and -imido complexes reveals unusual doubly degenerate electronic ground states

Phylogenetic diversity contributes more to sediment magnetism than abundance during incubation of iron-reducing sediment from a non-active volcanic lake in Northeast China.

This study aimed to analyse bacterial community and biomineralization products from Wudalianchi non-active volcanic field and the relationship between magnetization and bacterial community. Eighteen sediment samples obtained from Wenbo Lake, high-throughput sequencing and quantitative PCR (qPCR) were separately employed to investigate the bacterial community composition dynamics and abundance variation of the sediment sample with the highest iron-reducing capacity during incubation. The mineralization products were characterized by transmission electron microscopy, scanning electron microscopy, X-ray diffraction (XRD), Raman spectroscopy, vibrating sample magnetometer (VSM) and variable-temperature magnetism analyses. The results showed that the highest iron reduction rate was 98·06%. Seven phyla were identified as dominant bacterial phyla during the incubation process. Iron-reducing bacteria (FeRB) including Geobacter, Desulfosporosinus and Clostridium were involved in the iron mineralization process. The 16S rDNA copy numbers of sediment decreased quickly and then stayed steady during the incubation. Bacteria with rod-shaped and spheroid species were involved in extracellular iron reduction to produce magnetic particles with massive aggregation and columnar structures on the mineral surface morphologies. The materials produced by the microbial community over the incubation period were sequentially identified as siderite, magnetite and maghemite. The magnetism of the mineral samples gradually increased from 0·31748 to 33·58423emug-1 with increased incubation time. The final products showed relatively stable magnetism under 0-400K. Meanwhile, the saturation magnetization (MS ) of the mineralized substance was tightly associated with bacterial diversity (P<0·05). Bacterial community varied during incubation of iron-reducing sediment of volcanic lake. Various iron mineral crystals were in turn formed extracellularly by FeRB. The magnetism of mineralized products was tightly associated with bacterial community. These results not only help us to better understand the iron mineralization of FeRB in the volcanic lake sediments but also provide basic information for the future application of FeRB in environmental bioremediation.

Experimental and Theoretical Evidence for an Unusual Almost Triply Degenerate Electronic Ground State of Ferrous Tetraphenylporphyrin.

Iron porphyrins exhibit unrivalled catalytic activity for electrochemical CO2-to-CO conversion. Despite intensive experimental and computational studies in the last 4 decades, the exact nature of the prototypical square-planar [FeII(TPP)] complex (1; TPP2- = tetraphenylporphyrinate dianion) remained highly debated. Specifically, its intermediate-spin (S = 1) ground state was contradictorily assigned to either a nondegenerate 3A2g state with a (dxy)2(dz2)2(dxz,yz)2 configuration or a degenerate 3Egθ state with a (dxy)2(dxz,yz)3(dz2)1/(dz2)2(dxy)1(dxz,yz)3 configuration. To address this question, we present herein a comprehensive, spectroscopy-based theoretical and experimental electronic-structure investigation on complex 1. Highly correlated wave-function-based computations predicted that 3A2g and 3Egθ are well-isolated from other triplet states by ca. 4000 cm-1, whereas their splitting ΔA-E is on par with the effective spin-orbit coupling (SOC) constant of iron(II) (≈400 cm-1). Therfore, we invoked an effective Hamiltonian (EH) operating on the nine magnetic sublevels arising from SOC between the 3A2g and 3Egθ states. This approach enabled us to successfully simulate all spectroscopic data of 1 obtained by variable-temperature and variable-field magnetization, applied-field 57Fe Mössbauer, and terahertz electron paramagnetic resonance measurements. Remarkably, the EH contains only three adjustable parameters, namely, the energy gap without SOC, ΔA-E, an angle θ that describes the mixing of (dxy)2(dxz,yz)3(dz2)1 and (dz2)2(dxy)1(dxz,yz)3 configurations, and the ⟨rd-3⟩ expectation value of the iron d orbitals that is necessary to estimate the 57Fe magnetic hyperfine coupling tensor. The EH simulations revealed that the triplet ground state of 1 is genuinely multiconfigurational with substantial parentages of both 3A2g (<88%) and 3Eg (>12%), owing to their accidental near-triple degeneracy with ΔA-E = +950 cm-1. As a consequence of this peculiar electronic structure, 1 exhibits a huge effective magnetic moment (4.2 μB at 300 K), large temperature-independent paramagnetism, a large and positive axial zero-field splitting, strong easy-plane magnetization (g⊥ ≈ 3 and g∥ ≈ 1.7) and a large and positive internal field at the 57Fe nucleus aligned in the xy plane. Further in-depth analyses suggested that g⊥ ≫ g∥ is a general spectroscopic signature of near-triple orbital degeneracy with more than half-filled pseudodegenerate orbital sets. Implications of the unusual electronic structure of 1 for CO2 reduction are discussed.

Cobalt halide complexes of 2-, 3- and 4-methoxyaniline: Syntheses, structures and magnetic behavior

A family of six cobalt(II) compounds of the general formula (nMeO-C6H4NH2)2CoX2, (X = Cl, Br; nMeO-C6H4NH2 = 2-MeO-, 3-MeO-, or 4-MeO-aniline) has been prepared and the compounds characterized by combustion analysis, IR, single-crystal X-ray diffraction and variable temperature magnetization measurements [(n-MeOC6H4NH2)2CoX2, (1, n = 2, X = Cl; 2, n = 2, X = Br; 3, n = 3, X = Cl; 4, n = 3, X = Br; 5, n = 4, X = Cl; 6, n = 4, X = Br]. Although the six compounds crystallize in a variety of space groups, they are all isocoordinate. The compounds are slightly distorted tetrahedra. In all compounds, hydrogen bonds and short intermolecular X…Co contacts link the molecules into chains. For 3–6, short halide…halide contacts, in some cases short enough to be considered halogen bonds, further link the chains into layer structures. The complexes have also been studied via variable temperature magnetic susceptibility measurements. All six compounds exhibit antiferromagnetic exchange and show maxima in χ in the range 2–5 K. They have been fit to a variety of models incorporating single-ion anisotropy (SIA), and/or Heisenberg or Ising 1D- and 2D-systems. The results indicate that both antiferromagnetic superexchange and SIA are likely present in all compounds to some degree, but their relative contributions vary greatly. The potential superexchange pathways are discussed in terms of the observed magnetic properties and structures.

Multiresponsive Spin Crossover Driven by Rotation of Tetraphenylborate Anion in an Iron(III) Complex

Dynamic molecular materials, which involve mechanical motions in crystals, usually exhibit tunable properties related to conformational polymorphs. Herein, we describe a solvent-free molecular crys...

Ga2.52V2·48O7·33(OH)0.67, a synthetic member of the nolanite/akdalaite-type family of oxyhydroxides containing trivalent vanadium

The oxyhydroxide Ga2.52V2·48O7·33(OH)0.67 is prepared by reaction between Ga metal and Na3VO4 in a 1:1 monoethanolamine:water mixture at 240 ​°C. Powder neutron diffraction shows the material to be isostructural with the minerals nolanite and akdalaite, with cations occupying tetrahedral and octahedral interstitial sites in a hexagonal close-packed array of oxide/hydroxide (P63mc, a ​= ​5.7906(2) Å, c ​= ​9.2550(5) Å). Rietveld refinement against the data shows that Ga preferentially occupies tetrahedral sites, as well as some octahedral sites, and hence all V is octahedrally coordinated. The oxidation state of vanadium is confirmed as close to V3+ using V K-edge X-ray absorption near-edge structure spectroscopy, consistent with the refined chemical composition. The material is metastable, dehydrating around 300 ​°C and then decomposing above 500 ​°C, as shown by thermogravimetric analysis and thermodiffraction. The oxide Ga2.52V2.48O8 produced after dehydration at 300 ​°C is shown to contain a larger proportion of V4+ than the parent oxyhydroxide, to ensure charge balance, but the essential hexagonal structure is maintained. Variable temperature magnetisation measurements show that although both materials appear to obey the Curie-Weiss law at high temperatures, at low temperatures the inverse susceptibility curves are non-linear. There is, however, no evidence for strong magnetic exchange and the extracted effective moments are consistent with the presence of more V3+ in the oxyhydroxide compared to the oxide.

Metal-directed supramolecular architectures based on the bifunctional ligand 2,5-bis(1H-1,2,4-triazol-1-yl)terephthalic acid.

By the solvothermal reactions of 2,5-bis(1H-1,2,4-triazol-1-yl)terephthalic acid (H2L) with transition-metal ions, two novel polymeric complexes, namely, poly[diaqua[μ4-2,5-bis(1H-1,2,4-triazol-1-yl)terephthalato]cobalt(II)], [Co(C12H6N6O4)(H2O)2]n, (1), and poly[[diaqua[μ4-2,5-bis(1H-1,2,4-triazol-1-yl)terephthalato]nickel(II)] dihydrate], {[Ni(C12H6N6O4)(H2O)2]·2H2O}n, (2), were isolated. Both polymers have been characterized by FT-IR spectroscopy, elemental analysis and single-crystal X-ray diffraction analysis. The complexes have similar two-dimensional layered structures and coordination modes. Furthermore, the two-dimensional layered structures bear distinct intermolecular hydrogen-bonding interactions and π-π stacking interactions to form two different three-dimensional supramolecular networks based on 44-subnets. The structural variation depends on the nature of the metal cations. The results of variable-temperature magnetization measurements (χMT-T and χM-1-T) show that complexes (1) and (2) display antiferromagnetic behaviour.