Binuclear cyano-bridged complex derived from [MnIII(salpn)] and [FeIII(CN)6]: Synthesis,structure and magnetic properties

The reaction of the neutral [Mn(salpn)C(CN)₃(H₂O)] (salpn^2 − = N,N^′-1,3-propylenebis(salicylideneiminato) dianion) with [Fe^III(CN)₆]^3 − in the presence of strong oxidizer (NH₄)₂S₂O₈ yields a binuclear anion complex [NH₃CH₂CH₂CH₂NH₃]^2 +{[Mn^III(salpn)(H₂O)][Fe^III(CN)₆]}^2 − (1). Its structure, DC and AC susceptibility have been studied. Frequency dependence of the AC susceptibility characteristic for single-molecule magnets has been found.     

Photoredox reactions of binuclear iron(II) and (III) disulfide complexes. Disulfide as CT acceptor and donor

In analogy to peroxide, disulfide is an oxidant as well as a reductant. Accordingly, as a ligand of a reducing metal center, low-energy MLCT transitions can occur, while with oxidizing metals low-energy LMCT transitions should be observed. Such MLCT and LMCT excitations are expected to induce redox reactions. The complexes [CpFe(II)(CO)₂]₂μ-S₂ (CpC₅H₅) and {[Fe(III)(CN)₅]₂μ-S₂}^6 − are suitable examples to explore this behavior.     

Synthesis,structure and magnetic properties of spinel ferrite (Ni,Cu, Co)Fe2O4 from low nickel matte

Spinel ferrite (Ni, Cu, Co)Fe₂O₄ was synthesized from the low nickel matte by using a co-precipitation-calcination method for the first time. The influences of the added amount of NiCl₂·6H₂O, calcination temperature and time on the structure and magnetic properties of the as-prepared ferrites were studied in detail by X-ray diffraction (XRD), Scanning electron microscopy (SEM), Raman spectroscopy, and Vibrating sample magnetometer (VSM). It is indicated that pure (Ni, Cu, Co)Fe₂O₄ with cubic phase could be obtained under the experimental conditions (NiCl₂·6H₂O added amount of 3.0: 100 g mL⁻¹, calcination temperature from 800 to 1000 °C and calcination time from 1 to 3 h). With increasing calcination temperature and time, saturation magnetization (M_S) of the synthesized (Ni, Cu, Co)Fe₂O₄ increased and the coercivity (H_C) decreased. Under the optimum conditions (i.e. NiCl₂·6H₂O added amount of 3.0: 100 g mL⁻¹, 1000 °C, 3 h), the M_S and H_C values of the product were approximately 46.1 emu g⁻¹ and 51.0 Oe, respectively, which were competitive to those of other nickel ferrites synthesized from pure chemical reagents. This method explores a novel pathway for efficient and comprehensive utilization of the low nickel matte.     

pH-controlled the formation of 4-sulfocalix[4]arene-based 1D and 2D coordination polymers

Three manganese/4-sulfocalix[4]arene complexes, namely, {H[(C₂₈H₂₀O₁₆S₄)Mn(H₂O)₄Mn_0.5(H₂O)₂]}_n ·6nH₂O (1), {NH₄[(C₂₈H₂₀O₁₆S₄)Mn(H₂O)₄Mn_0.5(H₂O)₂]}_n · 5nH₂O (2), [(C₂₈H₂₀O₁₆S₄)Mn₂(H₂O)₈]_n · 6nH₂O (3), have been synthesized under different pH conditions. Complex 1, which exhibits a one-dimensional (1D) structure, is formed at [H⁺] = 2.0 mol L⁻¹. Reaction at pH 4 leads to another one-dimensional (1D) coordination polymer of 2. At pH 5, a two-dimensional (2D) coordination polymer of complex 3 is formed, showing clearly structural effects on pH response.     

Design,synthesis, structure and magnetic behavior of a high spin binuclear Fe(III) complex of N-(1-ethanol)-N,N-bis(3-tert-butyl-5-methyl-2-hydroxybenxyl) amine

The Mannich reaction of 2-aminoethanol, 2-tert-butyl-4-methylphenol, and formaldehyde at the ratio sets of 1:2:2 provided a new ligand, N-(1-ethanol)-N,N-bis(3-tert-butyl-5-methyl-2-hydroxybenxyl)amine (H₃L). In the presence of base, H₃L reacted with FeCl₃·6H₂O to form a dinuclear Fe(III) complex [Fe₂L₂] 1. The value of μ_eff at room temperature (5.95 μ_B), is much less than the expected spin-only value (8.37 μ_B) of two high spin (hs) Fe³⁺ (S = 5/2) ions [μ = g[∑ ZS(S + 1)]^1/2], indicating there were strong interactions between Fe³⁺ ions. The effective magnetic moment (μ_eff) decreased abruptly with cooling to a minimum value of 0.1 μ_B at 2 K. It was worth noting that Fe³⁺ ions of 1 exhibited thermally induced quartet ? doublet spin transitions, and these transitions were abrupt. The magnetic behaviors of 1 denoted the occurrence of intramolecular anti-ferromagnetic interactions. J (? 13.58 cm^? 1) agrees with the result from Gorun–Lippard equation, ? J (cm^? 1) = Aexp(BP(Å) = 12.9).     

Preparation of new heteronuclear (NH4)RE[FeII(CN)6]·nH2O complexes (RE = La,Ce, Pr,Nd, Sm,Gd, Dy,Y, Er,Lu) and their low-temperature decomposition for perovskite-type oxide

New heteronuclear (NH₄)RE^III[Fe^II(CN)₆]·nH₂O complexes (RE = La, Ce, Pr, Nd, Sm, Gd, Dy, Y, Er, Lu) were synthesized and their thermal decomposition products were investigated. The crystal structure of (NH₄)RE[Fe^II(CN)₆]·nH₂O would be a hexagonal unit cell (space group: P6₃/m), which was the same as that of La[Fe^III(CN)₆]·5H₂O. The hydration number n = 4 was estimated by TG results for all the RE complexes. The lattice constants depended on the ionic radius of the RE³⁺ ion for the heteronuclear complexes. The single phase of the perovskite type materials was directly obtained by decomposition of the heteronuclear complexes for RE = La, Pr, Nd, Sm, and Gd. A mixture of CeO₂ and Fe₂O₃ was formed for RE = Ce because of its oxidation to Ce⁴⁺. In the case of RE = Dy, Y, Er, and Lu complexes, the perovskite type materials formed at higher temperature via. mixed oxides such as RE₂O₃ and RE₄Fe₅O₁₃ due to the small RE³⁺ ionic radius.     

Synthesis and chemical reactivity of an Fe(III) metallacrown-6 towards N-donor Lewis bases

The iron(III) 18-azametallacrown-6 [Fe(ashz)(EtOH)]₆ (1) (ashz^3 − = trianionic derivative of N-acetylsalicylhydrazide), prepared upon reaction of [Fe₃(μ₃-O)(Piv)₆(H₂O)₃](Piv) (Piv = Bu^tCOO⁻) with H₃ashz, reacts with N-heterocyclic Lewis bases (B = pyridine, 4-methyl pyridine, 3-amino pyridine or imidazole), leading to the stable adducts [Fe(ashz)(B)]₆ (2 to 5, respectively) upon replacement of the labile ethanol ligand. All the compounds were characterized by elemental analysis, IR and ESI–mass spectroscopies and, for complexes 1 and the 3-amino pyridine adduct 4, also by X-ray crystallography. In both 1 and 4, the stereochemistry of the ligand imposes a propeller configuration of the metal cation which exhibits alternating Λ/Δ forms.     

Surface immobilization of Mo6I8 octahedral cluster cores on functionalized amorphous carbon using a pyridine complexation strategy

Tetrahedral amorphous carbon (a-C) films have been grown by pulsed laser deposition to investigate a liquid phase process for surface immobilization of electroactive [Mo₆Iⁱ₈]^4 + transition metal cluster cores using a complexation reaction with a pyridine-terminated alkyl monolayer covalently bonded to the a-C surface (Py^S–alkyl/a-C). These films are stable against thermally-assisted grafting of alkene molecules and the covalent CC interface provides a robust monolayer/a-C assembly. Octahedral [Mo₆Iⁱ₈]^4 + cluster cores with iodine inner ligands and labile triflate apical ligands [Mo₆Iⁱ₈(CF₃SO₃)^a₆]^2 − have been immobilized through partial complexation in apical positions by surface pyridine groups (Py^S). The remaining CF₃SO₃⁻ apical ligands of [Mo₆Iⁱ₈ (Py^S)^a_y(CF₃SO₃)^a_6 − y] cluster units were further substituted with bromopyridine (Py-Br) to obtain air stable surface with expected final composition [Mo₆Iⁱ₈ (Py^S)^a_y(Py-Br)^a_6 − y]. The yield of the different reaction steps is followed by X-ray photoelectron spectroscopy, providing cluster coverage Σ_Mo6I8 = 9 × 10¹² cm^− 2. Each [Mo₆I₈]^4 + cluster is bound to the carbon surface through multiple anchoring metal sites (N_PYR = 3 or 4), indicating that pyridine-terminated alkyl chains are flexible enough to accommodate four bonds. Electrical transport through Hg//Mo₆I₈–Py^S–alkyl/a-C/p-Si(111) junctions shows rectifying current–voltage characteristics but does not reveal any signature of cluster immobilization.     

MLCT interaction in [Rh(II)2(CO3)4]4 −( x L)

Complexes of the type [Rh^II₂(CO₃)₄(H₂O)L]^n − with L = N-methylpyrazinium⁺ and 1-heptyl-4-(4-pyridinyl)pyridinium⁺ cations display intense long-wavelength (Rh(II) to L) MLCT absorptions. With L = H₂O, MLCT absorptions are not identified, but the photoreactivity of the complex in aqueous solution supports the assumption that (Rh(II) to CO₃^2 −) MLCT excited states are accessible. Upon irradiation with white light, Rh(II) is photooxidized while carbonate is reduced to CO. The efficiency of this photolysis is very low. However, the occurrence of this photoredox reaction is, nevertheless, of general interest with regard to the photochemical reduction of CO₂.     

From tetranuclear cluster with single-molecule-magnet behavior to 1D alternating spin-canting chain in a Fe(III)–Mn(III) bimetallic system

A tetranuclear cluster and an alternating zigzag chain were synthesized via rational assembly of the same cyanometalate building blocks with different Mn(III) Schiff bases possessing varying proportions of sterically hindered groups causing steric hindrances. The tetranuclear cluster [(Tp*)Fe(CN)₃]₂[Mn(salen)]₂·H₂O [1; [(Tp*)Fe(CN)₃]⁻ [Tp* = hydrotris(3,5-dimethylpyrazol-1-yl) borate], salen = N,N′-ethylenebis(salicylideneiminato) dianion] was formed with Schiff bases possessing smaller steric hindrances, whereas the one-dimensional alternating zigzag chain {[(Tp*)Fe(CN)₃Mn(salcyen)]·2CH₃OH·H₂O}_n [2; salcyen = N,N′-(1,2-cyclohexanediylethylene)bis(salicylideneiminato) dianion] was formed with Schiff bases possessing larger steric hindrances. Magnetic measurements revealed that 1 exhibits single-molecule-magnet behavior with dominant ferromagnetic interactions, whereas 2 exhibits spin-canting behavior with dominant antiferromagnetic interactions.     

A novel polyoxometalate-based metal-organic compound constructed from an unprecedented [Ag8(Hpyttz)4(H2pyttz)2] cluster and an in-situ [VW12O40]3 − anion

A novel polyoxometalate (POM)-based metal-organic compound constructed from a multinuclear Ag^I cluster and Keggin-type [VW₁₂O₄₀]^3 − anion, [Ag₄(Hpyttz)₂(H₂pyttz)][HVW₁₂O₄₀]·3H₂O (1) (H₂pyttz = 5′-(pyridin-4-yl)-1H,2′H-3,3′-bi(1,2,4-triazole), was hydrothermally synthesized and characterized by IR spectroscopy, TG analysis, powder and single-crystal X-ray diffraction. In compound 1, [VW₁₂O₄₀]^3 − (VW₁₂) was in-situ transformed from [SiW₁₂O₄₀]^4 − anion. Eight Ag^I ions were connected by six Hpyttz/H₂pyttz ligands with three coordination modes forming an unprecedented [Ag₈(Hpyttz)₄(H₂pyttz)₂] cluster, which connected with six VW₁₂ anions to construct a 2-D double-layer (3,6)-connected network with {4³}₂{4⁶.6⁶.8³} topology. Moreover, the photocatalytic activity of 1 has been investigated.     

A cyanide-bridged two-dimensional grid-like FeIII–CoII complex based on the pentacyanideferrite(III) building block

A cyanide-bridged Fe^III–Co^II heterometallic complex {[Fe(1-CH₃im)(CN)₅][Co(H₂O)₂]}n·3H₂O (1-CH₃im = 1-methylimadazole) (2) has been synthesized by the reaction of Co^II(ClO₄)₂·6H₂O with the pentacyanideferrite(III) building block (Ph₄P)₂[Fe^III(1-CH₃im)(CN)₅]·4.5H₂O (1). X-Ray single crystal diffraction analysis shows that complex 2 has a two-dimensional (2D) grid-like structure. Magnetic investigations show that complex 2 displays long-range antiferromagnetic ordering with T_N = 9.45 K. The typical metamagnetic behaviors were observed with the critical field of ca. 4000 Oe at 1.82 K.     

A mixed-spin Fe(II) tetranuclear cluster: Preparation,structure and magnetic property

A tetranuclear ferrous cluster, [(phen)₂Fe(II)(CN)₂Fe(II)(bpqa)]₂(PF₄)₄ · H₂O · (CH₃OH)₂ (abbreviated as 1-(PF₆)₄) (bpqa = bis(2-pyridylmethyl)(2-quinolylmethyl)amine, phen = 1,10-phenanthroline), has been synthesized via self-assembly reaction. Single-crystal X-ray diffraction analysis shows that 1-(PF₆)₄ is a tetranuclear cyanide-bridged ferrous cluster, which is crystallized in centrosymmetric C2/c space group of monoclinic crystal system. The temperature (5–300 K) dependent magnetic susceptibility of 1-(PF₆)₄ corresponds to a mixed-spin state with two high spin and two low spin Fe(II) ions within the cluster.     

Two organic–inorganic hybrid materials based on the penta-nuclear {MMn4} (M = W and Mo) heterometallic clusters and Schiff-base ligands

Two organic–inorganic hybrid compounds with the formula {[Mn^III(Salen)(H₂O)]₄MoO₄}·Cl₂·16H₂O (1) and {[Mn^III(Salen)(H₂O)]₄WO₄}·(CH₃COO)₂·11H₂O (2) (Salen = Di-[2-hydroxyl-3-methoxyl-benzaldehyde] ethylenediamine) have been synthesized and structurally characterized by IR, UV–vis spectroscopy, TG analysis and single crystal X-ray diffraction. Structural analysis revealed that compounds 1 and 2 consist of a [MoO₄]^2 − or [WO₄]^2 − building unit and four {[Mn^III(Salen)(H₂O)]⁺ metal–organic moieties, respectively. In the crystal structure, the [MoO₄]^2 − or [WO₄]^2 − tetrahedra coordinated with four Mn^III ions, resulting in the penta-nuclear heterometallic tetrahedra cluster compounds, which were rarely observed in the Mn-Salen system. Magnetic study revealed that there was antiferromagnetic coupling in the two compounds.     

Photochemical reductive elimination of [PtIV(NH3)4(NH2)Cl]2 +: Photogeneration of hydrazine

When [Pt^IV(NH₃)₅Cl]^3 + is deprotonated the complex [Pt^IV(NH₃)₄(NH₂)Cl]^2 + is formed. Upon NH₂⁻ → Pt^IV LMCT excitation (λ_irr > 250 nm) a reductive elimination takes place: [Pt^IV(NH₃)₄(NH₂)Cl]^2 + → [Pt^II(NH₃)₃Cl]⁺ + N₂H₄ + H⁺. Since Pt(II) ammine complexes can be reoxidized to Pt(IV) by H₂O₂ it is suggested that in a cyclic process the overall reaction could proceed according to the equation: 2 NH₃ + H₂O₂ → N₂H₄ + 2 H₂O.     

X-ray single-crystal structure and magnetic properties of KMn(H2O)5Ru2(CO3)4·5H2O: A layered soft magnet

The temperature manipulation induces the aggregation of Ru₂(CO₃)₄^3 − paddle-wheel precursors and Mn^2 + ions in lower temperature ~ 10 °C forming layer structural complex, K[Mn(H₂O)₄Ru₂(CO₃)₄]·5H₂O (1). It composes of new negative layer {Mn(H₂O)₅Ru₂(CO₃)₄}_nⁿ⁻, and magnetic exchanges between spin centers result in ordering below 3.8 K. The observed critical temperature is like the previously reported 3D hetero-metallic carbonates H_0.3K_0.7Mn[Ru₂(CO₃)₄](H₂O)_5.5, which demonstrates that it is independent of the interlayer connecting in such heterometallic complexes based on square-grid layer {Ru₂(CO₃)₄}_n³ⁿ⁻.     

Heterometallic sulfide cluster [Ag6Sn6S20]10 −: Solvothermal syntheses and characterizations of silver thiostannates with lanthanide complex counter cations

Novel organic hybrid silver thiostannates [Hen]₄[Ln(en)₄]₂[Ag₆Sn₆S₂₀]·3en (Ln = Er, 1; Tm, 2; Yb, 3) were prepared by the reactions of Ln₂O₃, Ag, Sn and S in ethylenediamine (en) under solvothermal conditions. Six SnS₄ tetrahedra and six AgS₃ triangles are connected into the heterometallic sulfide cluster [Ag₆Sn₆S₂₀]^10 − via edge-sharing. In the [Ag₆Sn₆S₂₀]^10 − cluster, a hexanuclear Ag₆S₆ core is enclosed by two Sn₃S₁₀ fragments. The Ag₆S₆ core is the first As–S cluster stabilized by inorganic SnS₄ ligands. In 1–3, all Ln^3 + ions are in 8-fold coordination environments that involved four bidentate en ligands, forming bicapped trigonal prisms. Compounds 1–3 show well-defined absorption edges with band gaps in the range of 2.18–2.47 eV.     

Heat generation properties in AC magnetic field for Y3Fe5O12 powder material synthesized by a reverse coprecipitation method

Ferrimagnetic Y₃Fe₅O₁₂ powder was synthesized by a reverse coprecipitation method in order to study its heat generation property in an AC magnetic field. An orthorhombic YFeO₃ phase having a small particle size (<100 nm) was obtained for the samples calcined at a low temperature. The maximum heat generation ability in an AC magnetic field was obtained for the Y₃Fe₅O₁₂ ferrite powder by calcination at 1100 °C. The heat generation ability was reduced for the samples calcined at a higher temperature. The particle growth with the formation of the cubic single phase might influence the heat generation ability. The heat generation ability and the hysteresis loss value were proportional to the cube of the magnetic field (H³), because the coercivity value of the B–H curve was proportional to the square of the amplitude of the AC magnetic field (H²). The heat generation ability (W g⁻¹) of the Y₃Fe₅O₁₂ sample sintered at 1100 °C can be expressed by the equation 2.2×10⁻⁴∙f∙H³ using the frequency (f/kHz) and the magnetic field (H/kA m⁻¹), which has the highest heat generation ability of the reported magnetic materials. The hysteresis loss value for the B–H curve agreed with the heat generation ability of the samples calcined at 1100 °C and lower temperatures.     

C5H14NO · ZnCl(HPO3), an unexpected product from an ionic-liquid synthesis

C₅H₁₄NO · ZnCl(HPO₃) arose from an unexpected reaction in which a component of the ionic liquid mixed solvent was incorporated into a hybrid structure in which cholinium (C₅H₁₄NO⁺) cations interact with [ZnCl(HPO₃)]⁻ macroanionic layers by way of O–H⋯O hydrogen bonds. The inorganic layers display a 4 · 8² topology.     

Hexachloroplatinate(IV) anion-induced cucurbit[5]uril and cucurbit[8]uril supramolecular assemblies with linear channels

Two Q[n]-based porous compounds, Q[5]·[PtCl₆]^2 −·2H₃O·12H₂O and 2Q[8]·[PtCl₆]^2 −·2H₃O·74H₂O in cooperating the hexachloroplatinate(IV) anion ([PtCl₆]^2 −) as an inorganic structure directing agent are demonstrated. The driving forces for the formation of such novel Q[n]-based porous compounds are considered to be the outer surface interactions of Q[n]s, including dipole interactions between Q[n]s and ion-dipole interactions between [PtCl₆]^2 − anions and Q[n]s. Moreover, the Q[5]-based porous compound displays absorption distinctness for tetrachloromethane, whereas the Q[8]-based porous compound displays absorption distinctness for methanol.