A convenient MnIII starting material for the synthesis of homo- and heterometallic manganese carboxylate clusters: Mn9 and Mn10−xFex complexes

The use of a convenient source of Mn^III ions, namely the [Mn(OR)(O₂CR′)₂]_n (R = H, Me, and R′ = Me, Bu^t) family of 1-D coordination polymers, afforded two new enneanuclear and decanuclear molecular clusters, homometallic [Mn₉O₇(O₂CBu^t)₁₃(MeCN)₂] (3) and heterometallic [Mn_10?xFe_x(OMe)₂₀(O₂CMe)₁₀] (x < 10) (4), respectively. Compound 3 was synthesized by a solvent-induced structural transformation, whereas complex 4 resulted from the reaction of [Mn(OH)(O₂CMe)₂]_n with an Fe^III source. The core of 3 comprises two [Mn₄O₂]⁸⁺ butterfly units and a [Mn₃O]⁷⁺ triangular unit fused together by sharing one Mn atom. Magnetic susceptibility measurements of 3 revealed dominant antiferromagnetic interactions within the molecule, and a ground state of S = 1 with many low-lying excited states. Complex 4 is a mixed Fe^III/Mn^III single-strand molecular wheel, which forms 3D nanotubular stacks arranged in a zig–zag fashion. The described work suggests that the [Mn(OR)(O₂CR′)₂]_n compounds represent excellent starting materials for Mn^III carboxylate cluster chemistry.     

Two-color emission of Zn2SiO4:Mn from ionic liquid mediated synthesis

Yellow emitting β-Zn₂SiO₄:Mn²⁺ and green emitting α-Zn₂SiO₄:Mn²⁺ nanoparticles are synthesized by nucleation applying a zinc-containing ionic liquid. As-prepared material is non-agglomerated and very uniform with a mean diameter of 32 nm. According to X-ray diffraction (XRD) two crystallographic different modifications of Zn₂SiO₄ can be realized by annealing of as-prepared and non-crystalline nanomaterial at 750 and 1000 °C. Surprisingly, these crystalline materials are still nanosized, non-agglomerated and redispersible. Scanning electron microscopy (SEM) and dynamic light scattering (DLS) confirm particle diameters of 18 nm (β-Zn₂SiO₄:Mn²⁺) and 14 nm (α-Zn₂SiO₄:Mn²⁺). Photoluminescence indicates Mn²⁺-related emission at an average wavelength of 579 nm and 528 nm, and a quantum yield of 7% and 12% for β-Zn₂SiO₄:Mn²⁺ and α-Zn₂SiO₄:Mn²⁺, respectively.     

Al-doped ZnO powdered materials: Al solubility limit and IR absorption properties

Al-doped ZnO powder was synthesized via the Pechini route with a doping rate varying from 1 to 4 mol.%. A solubility limit has been estimated under 0.3 mol.% of Al using X-ray diffraction refinements. The incorporation of aluminium into the ZnO lattice was investigated by ²⁷Al NMR, which suggests an extremely low amount of Al in a distribution of sites in ZnO. In order to assess the impact of such a low dopant amount, diffuse reflection experiments were performed for a wavelength range from 200 to 2500 nm. If the effect of doping was negligible for samples prepared at 850 °C, annealing at 1200 °C clearly reveals enhanced IR absorption properties for the doped samples, which are similar whatever be the nominal Al content.     

Structural and optical properties of sprayed Zn1−xMnxO films

In recent years the dilute magnetic semiconductors have received much attention due to the complementary properties of semiconductor and ferromagnetic behaviour. Zn_1−xMn_xO thin films have been synthesized by chemical spray pyrolysis at a substrate temperature of 400 °C with different manganese compositions that vary in the range, 0.0 ≤ x ≤ 0.25, on Corning 7059 glass substrates. The X-ray diffraction studies revealed that all the films were strongly oriented along the (002) orientation corresponding to the hexagonal wurtzite structure. The crystalline quality of the layers was found to decrease with the increase of x, however, no structural changes were observed over the ‘Mn’ composition range investigated. The optical absorption studies revealed that the energy band gap of the films followed the Vegard's law. The optical band gap of the films prepared at x = 0.15 was found to be ∼3.35 eV. The photoluminescence characteristics of Zn_1−xMn_xO films showed an emission peak at around 390 nm with a broad band about 530 nm. The details of these results were reported and discussed.     

Magneto-structural correlation and low temperature heat capacity of a Mn (III) quadridentate Schiff-base coordination compound

A new Mn (III) Schiff-base coordination compound, [Mn(L)(NCS)]₂ (H₂L = N,N′-bis(5-chlorosalicylidene)-1,2-diaminoethane), has been synthesized and characterized structurally and magnetically. The target compound is a phenoxo-bridged dimeric compound with the isothiocyanate coordinating in a usual bent mode. A magnetic susceptibility study reveals that the target compound exhibits antiferromagnetic intra-dimer coupling between Mn (III) ions. The low temperature heat capacity of the compound over the temperature range (2 to 300) K has been measured using the heat capacity option of a Quantum Design Physical Property Measurement System (PPMS). The thermodynamic functions in the experimental temperature range have been determined by curve fitting. The standard entropy and enthalpy of the as-prepared compound at T = 298.15 K have been calculated to be (924.52 ± 10.17) J · K⁻¹ · mol⁻¹ and (133.47 ± 1.47) kJ · mol⁻¹, respectively.     

A mixed-valence Mn6 cluster capped by nitronyl nitroxide units

A mixed-valence Mn₆ cluster, [Mn₆O₂(t-BuCO₂)₁₀(H₂O)(NNPy)₂] (2), has been synthesized by the assembly of [Mn₆O₂(t-BuCO₂)₁₀(THF)₄] · THF (1) with a nitronyl nitroxide radical molecule, 2-(p-pyridyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide (NNPy). Complex 2 consists of [Mn₆O₂]¹⁰⁺ core and two NNPy radical attachments, where the [Mn₆O₂]¹⁰⁺ core is composed of two Mn^III ions (i.e., the inner Mn ions) bridged by two μ₄-O²⁻ and four Mn^II ions (i.e., the outer Mn ions) surrounding the inner Mn^III ions via the two μ₄-O²⁻, forming an edge-shared double-tetrahedral polygon (vertices: Mn ions, centers: μ₄-O²⁻). Bridges by pivalate groups in μ₂- and μ₃-modes assist the coordination spheres around these Mn ions. Two of the outer Mn^II ions in trans position are, to the sixth coordination site, occupied by NNPy molecule (pyridine-N coordination). One of the outer Mn^II ions is occupied by a water molecule to complete octahedral geometry, but the rest of them is vacancy taking a square-pyramidal geometry. The variable-temperature direct current (DC) magnetic susceptibility was collected in the temperature range of 1.81 to 300 K at a 1 kOe appled field. The molar magnetic susceptibility (χ_M) steadily increases from 0.053 emu mol⁻¹ at 300 K to 0.29 emu mol⁻¹ at 20 K, showing a kink (peak), and then increases rapidly to 0.70 emu mol⁻¹ at 1.81 K. The profile of this magnetic behavior indicates that the intracluster spin cancellation takes place bellow 20 K to derive an S_Mn6 = 0 by strong antiferromagnetic interaction between Mn ions. This is consequently leading to paramagnetic isolation of only the two nitronyl nitroxide units as if remaining as exchange-uncorrelated spin carriers. The variable-temperature ESR spectra show a sharp signal below 30 K with g = 2.00, proving the presence of free nitronyl nitroxide radical, in which double integral of such signal obeys the Curie–Weiss law that follows the susceptibility result in the low-temperature region.     

High-spin molecules: A mixed-valence Mn6 octahedron with an S = 11 ground state

The employment of 1,1,1-tris(hydroxymethyl)ethane ligand in higher oxidation state Mn cluster chemistry has yielded a new hexanuclear, mixed-valence (II,III,IV) compound with a rare [Mn₆(μ₆-O)]¹⁸⁺ octahedral core. The Mn₆ molecule is completely ferromagnetically coupled and possesses an S = 11 ground state, the maximum for a Mn^II, 2Mn^III, 3Mn^IV species.     

Effect of irradiation on photoluminescence and optical absorption spectra of Li2B4O7:Mn and Li2B4O7:Ag single crystals

Effects induced by high-dose irradiation on manganese- and silver-doped Li₂B₄O₇ (lithium tetraborate, LTB) single crystals were monitored by photoluminescence and optical absorption spectroscopy. High-dose (1.0×10³ and 1.2×10⁴ Gy) irradiation of the samples was performed using high-energy, short-time (4 MeV, 2.6 μs) electron pulses of a linear electron accelerator. Changes in the oxidation states of dopants were revealed. Recharging of manganese Mn²⁺→Mn³⁺ and Ag⁺→Ag⁰ were observed. Ionization process Mn²⁺→Mn³⁺+e⁻ and creation of Ag⁰-nanoparticles are supposed.     

Electrochemical deposition of (Mn, Co)-codoped ZnO nanorod arrays without any template

(Mn, Co)-codoped ZnO nanorod arrays were successfully prepared on Cu substrates by electrochemical self-assembly in solution of 0.5 mol/l ZnCl₂–0.01 mol/l MnCl₂–0.01 mol/l CoCl₂–0.1 mol/l KCl–0.05 mol/l tartaric acid at a temperature of 90 °C, and these nanorods were found to be oriented in the c-axis direction with wurtzite structure. Energy dispersive X-ray spectroscopy and x-ray diffraction show that the dopants Mn and Co are incorporated into the wurtzite-structure of ZnO. The concentrations of the dopants, and the orientations and densities of nanorods can easily be well controlled by the current densities of deposition or salt concentrations. Magnetization measurement indicates that the prepared (Mn, Co)-codoped ZnO nanorods with a coercivity of about 91 Oe and a saturation magnetization (M_s) of about 0.23 emu/g. The anisotropic magnetism for the (Mn, Co)-codoped ZnO nanorod arrays prepared in solution of 0.5 mol/l ZnCl₂–0.01 mol/l MnCl₂–0.01 mol/l CoCl₂–0.1 mol/l KCl–0.05 mol/l tartaric acid with current density of 0.5 mA/cm² was also investigated, and the crossover where the magnetic easy axis switches from parallel to perpendicular occurs at a calculated time of about 112 min. The anisotropic magnetism, depending on the rod geometry and density, can be explained in terms of a competition between self-demagnetization and magnetostatic coupling among the nanorods.     

Magnetic and theoretical characterization of a ferromagnetic Mn(III) dimer

Reaction of 1,1,1-tris(hydroxymethyl)ethane (H₃thme) with the complex [Mn₂O₂(bpy)₄](ClO₄)₃ produces the dimeric species [Mn₂(Hthme)₂(bpy)₂](ClO₄)₂ in high yield. Magnetic measurements in the temperature range 1.8–300 K and in fields up to 7 T reveal weak ferromagnetic exchange between the metal centres with J = +2.13 cm⁻¹. A fit of the magnetization data, assuming only the ground state is populated, gives S = 4, g = 1.71 and D = −0.65 cm⁻¹. Low temperature single crystal measurements suggest the co-existence of SMM behaviour and strong intermolecular interactions. Density functional calculations also support a weak exchange interaction between the Mn ions.     

Anodization of Au thin film on Al in oxalic acid

An Au thin film, which was sputter-deposited on an Al substrate, was potentiostatically anodized in oxalic acid. The Au film was first anodized and a spongelike nanoporous film grew down to the interface between Au and Al. Then, the Al was anodized and a very thin and fine nanoporous alumina film was formed underneath the nanoporous Au. Under the same anodization conditions, the current density for Al was ~ 40 μA cm^− 2, less than 1% of that for Au (~ 30 mA cm^− 2). The growth rates of the nanoporous films were ~ 0.7 nm/min for Al and 26 nm/min for Au, indicating that the growth rate of nanoporous alumina was less than 3% of that of nanoporous Au. Al is suitable as the substrate for preparing nanoporous Au films because the electrochemical reactions of both the electrolyte and the substrate are significantly suppressed when the nanopores penetrate Au and the electrolyte reaches the substrate.     

Operando soft x-ray emission spectroscopy of LiMn2O4 thin film involving Li–ion extraction/insertion reaction

We developed an electrochemical in situ cell for soft x-ray emission spectroscopy (XES) to accurately investigate the redox reaction and electronic structure of transition metals in the cathode materials for Li–ion battery. The in situ cell consists of a Li–metal counter electrode, an organic electrolyte solution, and a cathode on a membrane window which separates the liquid electrolyte from high vacuum and can pass the incoming and emitted photons. In this study, the Mn 3d electronic structure of LiMn₂O₄ thin-film electrode was clarified by the operando XES. At the charged state, the XES spectrum changed significantly from the open-circuit-voltage (OCV) state, suggesting oxidation of the Mn^3 + component through Li–ion extraction. Upon discharge up to 3.0 V vs. Li/Li⁺, the XES spectrum almost returned to its profile at the OCV state with small difference, indicating the valence change of Mn: Mn^3.6 + → Mn^4 + → Mn^3.3 + corresponding to the OCV, charged, and discharged states.     

Electrochemical and magnetic properties of inorganic polymers constructed from Mn(II)/Co(II)-substituted heteropolymolybdates

Two inorganic polymers constructed from transition metal-substituted heteropolymolybdates, [(CH₃)₃NH]_5n[PMo₁₁MO₃₉]_n·xH₂O (M = Mn²⁺, x = n (1); M = Co²⁺, x = 2n (2)), have been synthesized in aqueous solutions and characterized by IR, TGA, and single-crystal X-ray diffraction analysis. Crystal data: 1, monoclinic, C2/c, a = 17.1322(7) Å, b = 17.6062(7) Å, c = 17.6459(7) Å, β = 103.2220(10)°, V = 5181.5(4) Å³ and Z = 4; 2, triclinic, P-1, a = 12.1986(7) Å, b = 13.0973(7) Å, c = 16.7736(9) Å, α = 97.1810(10)°, β = 98.5040(11)°, γ = 96.3920(10)°, V = 2606.5(2) Å³ and Z = 2. The cyclic voltammograms of 1 and 2 show irreversible redox peaks in DMF solution and there are three reversible couples after addition of 0.1 M H₂SO₄ aqueous solutions. The cyclic voltammograms of 1/2-modified carbon paste electrode (1-CPE/2-CPE) show two consecutive reversible two-electron redox processes. Especially, 2-CPE shows good electrocatalytic activity toward the reduction of nitrite and hydrogen peroxide. The magnetic properties of the two complexes have also been investigated.     

Complex formation between manganese(II), cobalt(II), nickel(II), copper(II) and a series of new ligands derived from N,N′-O-phenylenebis(salicylideneimine)

A series of new ligands derived from N,N′-O-phenylenebis(salicylideneimine) have been synthesized and characterized by spectrometric methods. Their protonation constants and the stability constants of their complexes with Mn²⁺, Co²⁺, Ni²⁺ et Cu²⁺ have been determined by potentiometric methods in a water–ethanol (90:10 v/v) mixture at a 0.2 mol l⁻¹ ionic strength (NaCl) and at 25.0 ± 0.1 °C. The Sirko program was used to determine the protonation constants as well as the binding constants of both species [M(HL)]⁺ and [ML]. The stability order obtained is in agreement with Irving–Williams series.     

Ferromagnetic interaction between [Ni(bdt)2]− anions in [Mn2(Saloph)2(μ-OH)][Ni(bdt)2](CH3CN)2

A new molecule-based magnetic material [Mn₂(Saloph)₂(μ-OH)][Ni(bdt)₂](CH₃CN)₂ was prepared by the metathesis of [Mn(Saloph)(H₂O)(ClO₄)] (S = 2) and TBA[Ni(bdt)₂] (S = 1/2). In the crystal, [Ni(bdt)₂]^? anions form square lattices which are separated from each other by the layers of antiferromagnetically coupled binuclear cations [Mn₂(Saloph)₂(μ-OH)]⁺. The magnetic susceptibility of the material coincides with the sum of the S = 2 van Vleck dimer model and S = 1/2 Heisenberg ferromagnetic square lattice model with 2J = ?92.4 and +4.5 K, respectively. The origin of the ferromagnetic interaction can be explained by the T-shaped intermolecular overlap mode of SOMOs which spreads to the ends of [Ni(bdt)₂]^? molecules.     

Size-controllable synthesis of spherical ZnO nanoparticles: Size- and concentration-dependent resonant light scattering

A new and simple direct precipitation method assisted with ultrasonic agitation was proposed for the preparation of spherical ZnO nanoparticles. The size of the ZnO nanoparticles, 10 nm to 85 nm, was tuned through controlling the calcination temperature and changing the ratio of the reactants. The resonant light scattering (RLS) of the ZnO nanoparticles dispersed/suspended in aqueous solution of Triton X-100 was studied under room temperature. It was found that the ZnO nanoparticles of different size or concentration all have a characteristic RLS peak at 387 nm. Under optimal conditions, the RLS intensity was proportional to the ZnO concentration in the range of 7.3 × 10^?8–1 × 10^?4 mol L^?1, while the cubic root of the RLS intensity was found to be proportional to the size of ZnO nanoparticles. Further, the quantitative relationship of the size of the ZnO nanoparticles versus the calcination temperature was derived, and this could be used to forecast/control the nano-size in the nano-ZnO preparation.     

Fe-doped SnO2 transparent semi-conducting thin films deposited by spray pyrolysis technique: Thermoelectric and p-type conductivity properties

In this paper, we report structural, electrical, optical, and especially thermoelectrical characterization of iron (Fe) doped tin oxide films, which have been deposited by spray pyrolysis technique. The doping level has changed from 0 to 10 wt% in solution ([Fe]/[Sn] = 0–40 at% in solution). The thermoelectric response versus temperature difference has exhibited a nonlinear behavior, and the Seebeck coefficient has been calculated from its slope in temperature range of 300–500 K. The Hall effect and thermoelectric measurements have shown p-type conductivity in SnO₂:Fe films with [Fe]/[Sn] ≥ 7.8 at%. In doping levels lower than 7.8 at%, SnO₂:Fe films have been n-type with a negative thermoelectric coefficient. The Seebeck coefficient for SnO₂:Fe films with 7.8 at% doping level has been obtained to be as high as +1850 μV/K. The analysis of as-deposited samples with thicknesses ～350 nm by X-ray diffraction (XRD) and scanning electron microscopy (SEM) has shown polycrystalline structure with clear characteristic peak of SnO₂ cassiterite phase in all films. The optical transparency (T%) of SnO₂:Fe films in visible spectra decreases from 90% to 75% and electrical resistivity (ρ) increases from 1.2 × 10^?2 to 3 × 10³ Ω cm for Fe-doping in the range 0–40 at%.     

A family of dodecanuclear Mn11Ln single-molecule magnets

A series of four isostructural dodecanuclear complexes [Mn^III₉Mn^II₂Ln^III(O)₈(OH)(piv)₁₆(NO₃)(CH₃CN)]·xCH₃CN·yC₇H₁₆ (piv = pivalate; x = ½, y = ¾, Ln = Tb (1); x = 2, y = ½, Ln = Dy (2), Ho (3), and Y (4)) has been prepared for which the structural motif described as ‘a lanthanide ion nested in a large manganese shell’ is observed. All compounds show out-of-phase signals in their ac susceptibilities, and their single-molecule magnet behaviour was confirmed by single-crystal micro-SQUID studies of 1-3 which show hysteresis loops of molecular origin at T < 1.0 K. The SMM behaviour observed in compounds 1-3 is more pronounced than that for 4, which contains the diamagnetic Y^III ion. This is principally the result of ferromagnetic coupling between the paramagnetic anisotropic Ln^III ions (Tb^III, Dy^III and Ho^III) and the manganese shell, which enhances the total spin ground state of the complexes.     

Crystal structure,electrical conductivity,thermal expansion and compatibility studies of Co-substituted lanthanum strontium manganite system

La_0.76Sr_0.19Mn_1?xCo_xO_3±δ, LSMCo_x (0 ≤ x ≤ 1) perovskite oxides were synthesized by conventional ceramic route. The effect of Co substitution for Mn on the crystal structure, electrical conductivity and thermal expansion properties was investigated. XRD indicated rhombohedral symmetry for the studied compositions at 1673 K. The lattice parameters so determined showed significant reduction in cell volume, which is attributed to smaller ionic radii of Co³⁺ ions. The results of electrical conductivity data indicated that the conductivity mechanism is by thermally activated hopping of small polarons between localized states corresponding to Mn or Mn and Co sites of different valence value. The conductivity decreases at all temperatures up to 40 mol% Co substitution while the energy of activation increases. This is possibly due to an increase in Jahn–Teller distortion, at an extent higher than the increase of the concentration of charge carriers. Thermal expansion coefficient values in the series increase with increasing Co content which has been explained on the basis of the changes in the spin states of the Co ions and the consequent changes in the ionic size with temperature. Solution route synthesis produces fine-size particles with better properties, consequently one composition from the above having enhanced requisite properties, viz. La_0.76Sr_0.19Mn_0.8Co_0.2O_3±δ was synthesized by sol–gel route. The sol–gel synthesized compound had crystallite size of ～30 nm at 1173 K obtained using Scherrer's equation. Thus the potential of these compounds as cathodes for solid oxide fuel cells (SOFCs) have been evaluated.As Ce_0.8RE_0.2O_2?δ (RE = Sm, Gd) are being investigated for their use as electrolytes in SOFCs, their mechanical compatibility as well as chemical compatibility with the potential cathode material from the above LSMCo_x series was also studied.     

Syntheses,structures and single-molecule magnetic behaviors of two dicubane Mn4 complexes

The reaction of MnX₂ · 4H₂O (X = Cl or Br) with 2,6-bis(hydroxymethyl)-4-methylphenol (H₃L) and NaOH in methanol solution yielded two tetranuclear manganese complexes, [Mn₄(HL)₄(MeOH)₄Cl₂] (1) and [Mn₄(HL)₄(MeOH)₄Br₂] (2). Both compounds crystallize in the monoclinic space group C₂/c with cell parameters: a = 26.0945(19) Å, b = 11.4999(8) Å, c = 21.2188(16) Å, β = 121.050(1)° and z = 4 for 1 · 2Et₂O; a = 25.8145(3) Å, b = 11.6734(2) Å, c = 21.3956(3) Å, β = 120.1277(6)° and z = 4 for 2 · 2Et₂O. Both complexes consist of a mixed-valence dicubane structure, which comprises two Mn^II and two Mn^III ions. Magnetic susceptibilities and magnetization of complexes 1 and 2 in the solid state indicate that two clusters have an S = 9 ground state. Frequency-dependent out-of-phase signals of alternating current magnetic susceptibilities were observed in the low temperature range (<3 K) for both complexes indicating a slow magnetic relaxation.