Double Helix of Icosahedra Structure and Spin Glass Magnetism of the δ-Co2.5Zn17.5-xMnx (x = 0.4-3.5) Pseudo-Binary Alloys.

We have synthesized δ-Co2.5Zn17.5-xMnx (x = 0.4-3.5) pseudo-binary alloys of 10 different compositions by a high-temperature solid-state synthetic route, determined their crystal structures and the Mn substitution pattern, and estimated the existence range of the δ-phase. The alloys crystallize in two chiral enantiomorphic space groups P62 and P64, where the basic atomic polyhedron of the chiral structure is an icosahedron and the neighboring icosahedra share vertices to form an infinitely long double helix along the hexagonal axis (like in the δ-Co2.5Zn17.5 parent binary phase). The alloys are pure δ-phase up to the Mn content x ≈ 3.5. The Mn atoms partially substitute Zn atoms at particular crystallographic sites located on the icosahedra. The study of magnetism was performed on the Co2.5Zn17.1Mn0.4 alloy with the lowest Mn content. Contrary to the expectation that structural chirality may induce the formation of a nontrivial magnetic state, a spin glass state with no relation to the structural chirality was found. The magnetic sublattice contains all of the necessary ingredients (randomness and frustration) for the formation of a spin glass state. Typical out-of-equilibrium dynamic phenomena of a spin system with broken ergodicity were detected below the spin freezing temperature Tf ≈ 8 K.

Photophysical Behavior of Triethylmethylammonium Tetrabromoferrate(III) under High Pressure.

The pressure-induced properties of hybrid organic-inorganic ferroelectrics (HOIFs) with tunable structures and selectable organic and inorganic components are important for device fabrication. However, given the structural complexity of polycrystalline HOIFs and the limited resolution of pressure data, resolving the structure-property puzzle has so far been the exception rather than the rule. With this in mind, we present a collection of in situ high-pressure data measured for triethylmethylammonium tetrabromoferrate(III), ([N(C2H5)3CH3][FeBr4]) (EMAFB) by unraveling its flexible physical and photophysical behavior up to 80 GPa. Pressure-driven X-ray diffraction and Raman spectroscopy disclose its soft and reversible structural distortion, creating room for delicate band gap modulation. During compression, orange turns dark red at ∼2 GPa, and further compression results in piezochromism, leading to opaque black, while decompressed EMAFB appears in an orange hue. Assuming that the mechanical softness of EMAFB is the basis for reversible piezochromic control, we present alternations in the electronic landscape leading to a 1.22 eV band narrowing at 20.3 GPa while maintaining the semiconducting character at 72 GPa. EMAFB exhibits an emission enhancement, manifested by an increase of photoluminescence up to 17.3 GPa, correlating with the onsets of structural distortion and amorphization. The stimuli-responsive behavior of EMAFB, exhibiting stress-activated modification of the electronic structure, can enrich the physical library of HOIFs suitable for pressure-sensing technologies.

Finding the True Catalyst for Water Oxidation at Low Overpotential in the Presence of a Metal Complex.

The design of molecular-based catalysts for oxygen-evolution reaction (OER) requires more investigations for the true catalyst to be found. First-row transition metal complexes are extensively investigated for OER, but the role of these metal complexes as a true catalyst is doubtful. Some doubts have been expressed about the role of first-row transition metal complexes for OER at high overpotentials (η > 450). Generally, the detection of the true catalyst has so far been focused on high overpotentials (η > 450) because at low overpotentials (η < 450), many methods are not sensitive enough to detect small amounts of heterogeneous catalysts on the electrode surface during the first seconds of the reaction. Ni(II) phthalocyanine-tetra sulfonate tetrasodium (1) is in moderate conditions (at 20-50 °C and pH 5-13) in the absence of electrochemical driving forces, which could make it noteworthy for OER. Herein, the results of OER in the presence of 1 at low overpotentials under alkaline conditions are presented. In addition, in the presence of Ni complexes, using an Fe ion is introduced as a new method for detecting Ni (hydr)oxide under OER. Our experiments indicate that in the presence of a homogeneous OER (pre)catalyst, a deep investigation is necessary to rule out the heterogeneous catalysts formed. Our approach is a roadmap in the field of catalysis to understand the OER mechanism in the presence of a molecular Ni-based catalyst design. Our results shown in this study are likely to open up new perspectives and discussion on many molecular catalysts in a considerable part of the chemistry community.

Structural Model and Spin-Glass Magnetism of the Ce3Au13Ge4 Quasicrystalline Approximant.

In a search for unconventional heavy-Fermion compounds with the localized 4f moments distributed quasiperiodically instead of a conventional distribution on a regular, translationally periodic lattice, we have successfully synthesized a stable Ce3Au13Ge4 Tsai-type 1/1 quasicrystalline approximant of the off-stoichiometric composition Ce3+xAu13+yGe4+z (x = 0.17, y = 0.49, z = 1.08) and determined its structural model. The structure is body-centered-cubic (bcc), with space group Im3̅, unit cell parameter a = 14.874(3) Å, and Pearson symbol cI174, and can be described as a bcc packing of partially interpenetrating multishell rhombic triacontahedral clusters. The cerium sublattice, corresponding to the magnetic sublattice, consists of a bcc packing of Ce icosahedra with an additional Ce atom in a partially occupied site (occupation 0.7) at the center of each icosahedron. The measurements of its magnetic properties and the specific heat have demonstrated that it is a regular intermetallic compound with no resemblance to heavy-Fermion systems. The partially occupied Ce2 site in the center of each Ce1 icosahedron, the mixed-occupied Au/Ge ligand sites between the Ce2 and Ce1 atoms, and the random compositional fluctuations due to nonstoichiometry of the investigated Ce3+xAu13+yGe4+z alloy introduce randomness into the Ce magnetic sublattice, which causes a distribution of the indirect-exchange antiferromagnetic interactions between the spins. Together with the geometric frustration of the triangularly distributed Ce moments, this leads to a spin-glass phase below the spin freezing temperature Tf ≈ 0.28 K.

A Carbonate-Templated Decanuclear Mn Nanocage with Two Different Silsesquioxane Ligands.

The mild reaction of the preorganized silsesquioxane precursor with Mn(II) acetate under ambient conditions results in a mixed-valent {MnII6MnIII4} nanocage (SD/Mn10) which is protected by both acyclic trimer [Si3] and cyclic tetramer [Si4]. Serendipitous capture of atmospheric CO2 as a µ5-carbonate anion placed at the center supports the formation of the cluster. The magnetic analysis reveals the strong antiferromagnetic interactions between Mn ions. Moreover, the drop-casting film of SD/Mn10 shows photoelectric activity indicating its great potential as a semiconductor for photoelectric conversion applications.

Copper(II)-Assisted Ligand Fragmentation Leading to Three Families of Metallamacrocycle.

We present an unprecedented copper(II)-assisted organic ligand fragmentation process under basic conditions leading to several ligands within three families of metallamacrocycle, Cu6, Cu8, and Cu16. The sequential multistep reaction include (i) the deprotonation of the starting alcohol, 1,2-bis(3,5-dimethyl-pyrazol-1-yl)ethane-1,2-diol (H2bdped) to its diolate bdped followed by complexation through six bonds (µ6) to three copper atoms in a ring, (ii) the breaking of the ethane-pyrazole C-N bonds by the different solvent alcohols to form 1-(3,5-dimethyl-pyrazol-1-yl)-2-methoxyethane-1,2-diolate (dpmed) or 2-(3,5-dimethyl-pyrazol-1-yl)-2-hydroxyacetate (dpet), while retaining coordination to the copper centers and (iii) the final step to ethane-1,1,2,2-tetraolate, C2H2O44- (et). Importantly, the latter product, only observed on two previous occasions, occupies the core of Cu6 and Cu16 through exceptionally eight coordination bonds (µ8). Its alkyl esters, 2-alkoxyethane-1,1,2-triolate (met, eet, and pet), also occupy the central parts of Cu8 but forming six bonds (µ6) instead. The other product, 3,5-dimethylpyrazolate (dp), acts as peripheral bridges (µ2) but it is not involved in coordination if the starting salt is copper acetate, this may be a consequence of acetate being a better µ2-chelating ligand. In the presence of an oxidizing agent, K2Cr2O7, C2H2O44- (et) is oxidized to oxalate, C2O42- (ox). Thus, an additional µ3-hydroxide and µ4-oxalate in Cu16 widen the complexity of the structures, not to mention the range of coordination geometries of the copper centers, though in the present cases they can be classed in only two types: distorted square-planar and square-pyramid. In addition to single-crystal crystallography, the results from different techniques such as IR, ESI-MS, optical UV-vis, and SQUID magnetometry help in the characterization of these rare metallamacrocycles made from unexpected and in situ generated ligands. We believe the results of the organic transformations are highly relevant to von Liebig's benzil-benzilic acid rearrangement.

Magnetoelectric Coupling Springing Up in Molecular Ferroelectric: [N(C2H5)3CH3][FeCl4].

A molecule-based ferroelectric triethylmethylammonium tetrachloroferrate(III) ([N(C2H5)3CH3][FeCl4]) powder was designed as a multifunctional material exhibiting excellent multiple bistability. Prepared by the slow evaporation method at room temperature, the compound crystallizes in the non-centrosymmetric assembly of hexagonal symmetry (P63mc space group) which undergoes a reversible temperature-triggered phase transition pinpointed at 363 K to the centrosymmetric packing within the P63/mmc space group. Aside from the inseparable role of the symmetry-breaking process smoothly unveiled from the X-ray powder diffraction data, a striking change in the dielectric permittivity observed during the paraelectric-to-ferroelectric phase transition directly discloses the bistable dielectric behavior-an exceptionally high increase in the dielectric permittivity of about 360% at 100 kHz across the heating and cooling cycles is direct proof showing the highly desirable stimuli-responsive electric ordering in this improper ferroelectric architecture. Due to the magnetically modulated physical properties resulting in the coupling of magnetic and electric orderings, the flexible assembly of [N(C2H5)3CH3][FeCl4] could be used to boost the design and development of novel magnetoelectric devices.

A Polyoxochromate Templated 56-Nuclei Silver Nanocluster.

Most of polyoxometallates (POMs) templated silver nanoclusters recorded so far are polyoxomolybdates and polyoxotungstates; however, as congeneric polyoxochromates, they are rarely observed in silver nanoclusters. Herein, a high-nuclearity polyoxochromate, (CrIII4CrVI8O36)12-, is uncovered in a novel silver nanocluster (SD/Ag56a) as an anion template. The mixed-valent (CrIII4CrVI8O36)12- consists of four edge-sharing CrIIIO6 octahedra and eight CrVIO4 tetrahedra, which are fused together by sharing one or two vertexes. The (CrIII4CrVI8O36)12- is the by far highest nuclearity polyoxochromate and is trapped by outer Ag56 bracelet-like shell coprotected by quaternary ligands including iPrS-, NapCOO- (2-naphthalenecarboxylate), CF3COO-, and CH3CN. The antiferromagnetic property and solution behavior of SD/Ag56a are discussed in detail.

An Octanuclear Cobalt Cluster Protected by Macrocyclic Ligand: In Situ Ligand-Transformation-Assisted Assembly and Single-Molecule Magnet Behavior.

Macrocyclic molecules with multiple coordination sites have been widely used as promising ligands to build polynuclear metal clusters; however, cyclic silsesquioxane-based metal clusters are still rare. Herein, we report a new octanuclear Co-silsesquioxane cluster [Co8(OH)2{(MeSiO2)6}2(bpy)2(Obpy)2] (SD/Co8c; SD = SunDi), wherein the Co8 disc-like core is sandwiched by two hexamethylcyclohexasiloxanolate ligands (MeSiO2)6 at two poles and finally encircled by two bpy (bpy = 2,2'-bipyridine) and two Obpy (HObpy = 6-hydroxy-2,2'-bipyridine) ligands at the equatorial region. Interestingly, both MeSi(OMe)3 and bpy undergo in situ transformations to generate hexameric cyclic (MeSiO2)6 and Obpy, respectively. The unusual hydroxylation of bpy and the OH- anion in the center of Co8 core provide additional binding sites to induce the formation of the larger cluster instead of the traditional hexanuclear cluster. The solution stability and fragmentation route in the gas phase were studied by cold-spray ionization and collision-induced dissociation mass spectrometry, respectively. Both results reveal that the Co8 core is quite stable in solution as well as in the gas phase, even with increased collision voltage. Magnetic susceptibility studies of SD/Co8c show the slow magnetization relaxation indicative of single-molecule magnet (SMM) behavior. This work not only presents the multiple in situ ligand-transformation-assisted assembly of polynuclear cobalt cluster but also provides some new insights into the magnetism-structure relationship for SMMs.

Nanocrystalline Antiferromagnetic High-κ Dielectric Sr2NiMO6 (M = Te, W) with Double Perovskite Structure Type.

Double perovskites have been extensively studied in materials chemistry due to their excellent properties and novel features attributed to the coexistence of ferro/ferri/antiferro-magnetic ground state and semiconductor band gap within the same material. Double perovskites with Sr2NiMO6 (M = Te, W) structure type have been synthesized using simple, non-toxic and costless aqueous citrate sol-gel route. The reaction yielded phase-pure nanocrystalline powders of two compounds: Sr2NiWO6 (SNWO) and Sr2NiTeO6 (SNTO). According to the Rietveld refinement of powder X-ray diffraction data at room temperature, Sr2NiWO6 is tetragonal (I4/m) and Sr2NiTeO6 is monoclinic (C12/m1), with average crystallite sizes of 49 and 77 nm, respectively. Structural studies have been additionally performed by Raman spectroscopy revealing optical phonons typical for vibrations of Te6+/W6+O6 octahedra. Both SNTO and SNWO possess high values of dielectric constants (341 and 308, respectively) with low dielectric loss (0.06 for SNWO) at a frequency of 1 kHz. These values decrease exponentially with the increase of frequency to 1000 kHz, with the dielectric constant being around 260 for both compounds and dielectric loss being 0.01 for SNWO and 0.04 for SNTO. The Nyquist plot for both samples confirms the non-Debye type of relaxation behavior and the dominance of shorter-range movement of charge carriers. Magnetic studies of both compounds revealed antiferromagnetic behavior, with Néel temperature (TN) being 57 K for SNWO and 35 K for SNTO.

Hexadecanuclear MnII2MnIII14 Molecular Torus Built from in Situ Tandem Ligand Transformations.

A mixed-valent hexadecanuclear manganese cluster, [MnII2MnIII14(trz)14(thetach)4(µ3-O)8(H2O)10](ClO4)6 (Mn16), containing two MnII and 14 MnIII ions, is constructed from mixed in situ generated ligands, 1,2,3-triazole (Htrz) and 1,3,5-tri(2-hydroxyethyl)-1,3,5-triazacyclohexane (H3thetach). Remarkably, both ligands were not initially added into the reaction system, and their formations involve the in situ ligand decomposition and subsequent condensation reactions. The core of Mn16 is an elongated torus comprised of eight Mn atoms and four [Mn2O2] subunits bridged by oxo or alkoxide. The high-resolution electrospray ionization mass spectrometry (HR-ESI-MS) of Mn16 dissolved in CH3CN indicates its structure remains intact as +3 and +4 species. Temperature and field dependent magnetization revealed predominantly antiferromagnetic exchange interactions within the cluster. The work provides one-pot synthesis of high-nuclearity manganese clusters using the ligands generated by in situ reactions in a tandem fashion.

Space Craft-like Octanuclear Co(II)-Silsesquioxane Nanocages: Synthesis, Structure, Magnetic Properties, Solution Behavior, and Catalytic Activity for Hydroboration of Ketones.

Two novel space craft-like octanuclear Co(II)-silsesquioxane nanocages, {Co8[(MeSiO2)4]2(dmpz)8} (SD/Co8a) and {Co8[(PhSiO2)4]2(dmpz)8} (SD/Co8b) (SD = SunDi; Hdmpz = 3,5-dimethylpyrazole), have been constructed from two similar multidentate silsesquioxane ligands assisted with a pyrazole ligand. The Co8 skeleton consists of eight tetrahedral Co(II) ions arranged in a ring and is further capped by two (MeSiO2)4 ligands up and down. The auxiliary dmpz- ligands seal the ring finally. Electrospray ionization mass spectrometry revealed SD/Co8a and SD/Co8b are highly stable in CH2Cl2. Magnetic analysis implies that SD/Co8a announces antiferromagnetic interactions between Co(II) ions. Moreover, both of them display good homogeneous catalytic activity for hydroboration of ketones in the presence of pinacolborane under mild conditions.

Self-Organization into Preferred Sites by MgII, MnII, and MnIII in Brucite-Structured M19 Cluster.

The search for functional materials, for example those aiming at microelectronics, magnetic recording, and catalysis, often ventures into mixed metal systems to achieve optimization of the properties. Thus, understanding site preference and self-organization is crucial but hard to implement. Herein, we present a system whereby MgII, MnII, and MnIII ions selectively locate exact positions within the Brucite-structured cluster, Mn13Mg6, [MnIII⊂MgII6⊂MnII9MnIII3( L)18(OH)12(N3)6](ClO4)6·12CH3CN, H L = 1-(hydroxymethyl)-3,5-dimethylpyrazolate). The MnIII being small (78 pm) takes up the core position; while 6 MgII (86 pm) are located in the inner ring, and the 9 large MnII (97 pm) and 3 MnIII occupy the outer ring. The factors (a) ionic radii, (b) regularity in coordination geometry, oxophilicity, and softness of MgII compared to MnII, and (c) Jahn-Teller distortion of MnIII may all be implicated synergistically. Electrospray ionization mass spectrometry reveals the M19 disc remains an integral unit when crystals are dissolved, and exchange between Mg and Mn occurs within the disc during its formation. Diamagnetic MgII doping insulates the magnetic exchange between the central MnIII and those in the outer ring, thus giving an overall antiferromagnetic exchange interaction between nearest-neighbors of the outer ring. The work reveals the underlying rule for site-preference of main group metal versus transition metal in disc-like Brucite-structured cluster and provides an elegant new avenue to assemble heterometallic clusters in a stepwise fashion.

Diaquabis(2,2'-dipyridylamine)M(II) Terephthalate Dihydrates, M(II) = Ni, Co: Synthesis, Crystal Structures, Thermal and Magnetic Properties.

Two new isostructural M(II) (M = Ni, Co) complexes with 2,2'-dipyridylamine (dipya) and dianion of terephthalic acid (H2tpht), [M(dipya)2(H2O)2](tpht) ∙ 2H2O, have been synthesized by ligand exchange reaction and characterized by single-crystal X-ray diffraction, FTIR spectroscopy, TG/DSC analysis and magnetic measurements. The crystal structures of [M(dipya)2(H2O)2](tpht) ∙ 2H2O consist of discrete complex units in which M(II) adopts deformed octahedral geometries. Two dipya ligands and two water molecules are coordinated to M(II) atom, tpht acts as a counter ion, while additional two water molecules remained uncoordinated. By numerous hydrogen bonds, all structural fragments are connected in three different chains which extend along [100], [010] and [001] directions, giving as a result a complex 3D network. The stabilization of 3D structure is accomplished by non-covalent face to face π-π interactions among pyridyl ring of dipya and benzene ring of tpht from adjacent chains. Towards the applied magnetic field, the both complexes exhibited almost perfect paramagnetic behavior.

[Ag(OH2 )2 ][Ag(SO4 )2 ]: A Hydrate of a Silver(II) Salt.

When exposed to air at ambient conditions, AgSO4 slowly reacts with moisture, yielding AgSO4 ⋅H2 O. The crystal structure determination (powder data) shows that it may be described as [Ag(OH2 )2 ][Ag(SO4 )2 ], with some sulfate groups being shared between different Ag2+ cations, resembling in that way its Cu2+ analogue. [Ag(OH2 )2 ][Ag(SO4 )2 ], the first hydrate of a compound of Ag2+ , was extensively characterized using many physicochemical methods.

Canted Antiferromagnetism in Two-Dimensional Silver(II) Bis[pentafluoridooxidotungstate(VI)].

By slow reaction between colorless AgIW2O2F9 and elemental F2 in liquid anhydrous HF, violet platelike single crystals of Ag(WOF5)2 were grown. The crystal structure of Ag(WOF5)2 consists of layers built from Ag2+ cations bridged by [WOF5]- anions and not, as previously assumed, from infinite [AgII-F]+∞ chains and [W2O2F9]- anions. A majority (97%) of the disordered AgII cations are found with square-planar coordination of F/O ligands within the same layer, and they form additional long contacts with O/F atoms originating from the neighboring layers. The remaining 3% the of Ag(II) ions are coordinated only by F atoms in a square-planar fashion. The magnetic moments of Ag2+ from the same layer are almost perfectly antiferromagnetically aligned. Weak ferromagnetic interlayer interactions cause a small tilt (∼1.5°) of the magnetic moments, resulting in canted antiferromagnetism. Because of the lowering of the symmetry of [WOF5]- in the solid state, the vibrational spectra show more bands than expected for regular C4v symmetry. The electronic spectrum of Ag(WOF5)2 is reported and analyzed.

Local and Cooperative Jahn-Teller Effect and Resultant Magnetic Properties of M2AgF4 (M = Na-Cs) Phases.

The crystal structure, magnetic properties, heat capacity, and Raman spectra of double-perovskite M2AgF4 (M = K, K3/4Rb1/4, K1/2Rb1/2, K1/4Rb3/4, and Rb) phases have been examined, adding to the body of previous results for the M = Na, Cs derivatives. The results suggest that double-perovskite K2AgF4 adopts a disordered orthorhombic Bmab structure with an antiferrodistortive arrangement of the elongated and tilted [AgF6] octahedra rather than the structure with the ferrodistortive arrangement of compressed octahedra, as suggested previously (Mazej, Z.; Goreshnik, E.; Jaglicic, Z.; Gawel, B.; Lasocha, W.; Grzybowska, D.; Jaron, T.; Kurzydlowski, D.; Malinowski, P. J.; Kozminski, W.; Szydlowska, J.; Leszczynski, P. J.; Grochala, W. KAgF3, K2AgF4 and K3Ag2F7: important steps towards a layered antiferromagnetic fluoroargentate(II). CrystEngComm 2009, 11, 1702-1710). A re-examination of the previously collected single-crystal X-ray diffraction data confirms the current structure assignment, and it is also in agreement with recent theoretical calculations. High-field electron paramagnetic resonance spectra reaffirm the presence of elongated [AgF6] octahedra in the crystal structure of all M2AgF4 phases studied. The local structure of the M = K derivative is most complex, with regions of the sample that are quite orthorhombically distorted, whereas other regions more closely resemble the tetragonal phase. The mixed-cation K/Rb phases are also inhomogeneous, containing regions of the pure K compound and regions of another high-symmetry phase (likely tetragonal) of a mixed (Rb-richer) compound with unknown composition. The temperature-resolved phase diagram of all K/Rb phases has been established and positioned within the entire M = Na, K, Rb, Cs series.

A Pyridazine-Bridged Sandwiched Cluster Incorporating Planar Hexanuclear Cobalt Ring and Bivacant Phosphotungstate.

A planar hexanuclear cobalt ring was clamped by two bivacant α1-[PW10O37](9-) with the assistance of the pyridazine bridges to form a novel sandwiched Co(II)-polyoxometalate cluster compound, [Na(H2O)6][Co3(OH) (pydz)4(H2O)7][Co6(PW10O37)2(pydz)4(H2O)6]·43H2O (1; pydz = pyridazine).This cluster was identified by X-ray single-crystal diffraction, elemental analysis, Fourier transform IR and UV-visible spectroscopies, and cyclic voltammetry (CV). Structural analysis reveals that 1 comprises a hexahydrated sodium, a trinuclear [Co3(OH) (pydz)4(H2O)7](5+) cationic cluster, and an anionic [Co6(PW10O37)2(pydz)4(H2O)6](6-) sandwiched cluster, thus giving an intrinsical intercluster compound. The isolation of such cluster was dependent on the in situ transformation of trivacant [α-P2W15O56](12-) to α1-[PW10O37](9-) under the hydrothermal condition. The CV shows reversible multielectron waves from the redox of W(VI) in 1. Cluster 1 exhibits remarkable electrocatalytic activity toward the reduction of nitrite. Magnetism studies indicated a weak anti-ferromagnetic exchange interaction between Co(II) ions within 1.

Four Hybrid Materials Based on Preyssler P5W30 Polyoxometalate and First-Row Transition-Metal Complex.

Four Preyssler P5W30 based inorganic-organic hybrids, formulated as {[Cu12(pbtz)2(Hpbtz)2(OH)4(H2O)16][Na(H2O)P5W30O110]}·16H2O (1; H2pbtz = 5'-(pyridin-2-yl)-1H,2'H-3,3'-bi(1,2,4-triazole)), {[Cu10(ttbz)2(Httbz)4(OH)6(H2O)8][K(H2O)H2P5W30O110]}·30H2O (2; Httbz = 1-(tetrazo-5-yl)-4-(triazo-1-yl)benzene), {[Ni6(bpz)6(H2O)16][Na(H2O)H2P5W30O110]}·36H2O (3; bpz = 3,3',5,5'-tetramethyl-4,4-bipyrazole), {[Co4(bpz)6(H2O)9][K(H2O)H6P5W30O110]}·46H2O (4), have been isolated and structurally identified via microanalysis, thermogravimetry (TG), infrared (IR) spectroscopy, and X-ray single-crystal diffraction. Compound 1 exhibits a 3D binodal (3,6)-connected ant framework composed of dodeca-supported P5W30 polyoxometalate (POM) clusters and discrete [Cu6(pbtz)(Hpbtz)(OH)2(H2O)8] subunits. Compound 2 is a pillared-layer 3D network constructed from [Cu5(ttbz)(Httbz)2(OH)3(H2O)4] sheets pillared by individual P5W30 clusters. Compound 3 contains octa-supporting P5W30 POM clusters and novel [Ni6(bpz)6] crown-like metallamacrocycles, which construct a (4,4)-connected pts network. Compound 4 displays a complicated 3D (5,5)-connected {4(5)·6(4)·8}{4(5)·6(5)} network built by pentasupporting P5W30 POM clusters and discrete [Co4(bpz)6(H2O)9] subunits. In 1-4, the unified features are the Preyssler-type [P5W30O110] POM as the fundamental building block, which supports the transition-metal compounds with different modes to give the resultant diverse networks. The magnetism studies indicated antiferromagnetically coupled systems for the hexa- and pentanuclear Cu(II) units in 1 and 2, respectively. The electrochemical properties demonstrate that all compounds have electrocatalytic abilities toward the reduction of hydrogen peroxide. Furthermore, the catalytic activities of 1 in the cyanosilylation of aldehydes reaction have been investigated.

Template synthesis of single-phase δ(3)-MoN superconducting nanowires.

We demonstrate a new and effective method of producing single-phase superconducting δ3-MoN nanowires from bundled Mo6SyIz (8.2 ≤ y + z ≤ 10) nanowire templates in the presence of ammonia gas. Magnetic susceptibility and electrical resistance measurements confirm single-phase material synthesis. Measurements of four-contact resistance on single wires with diameters above 100 nm in a magnetic field are used to determine the critical field, while diameter dependence and magnetization measurements are used to investigate the homogeneity of the nanowires.