Hydrazine Ligand Research Articles

A two-dimensional ZnII coordination polymer constructed from benzene-1,2,3-tricarboxylic acid and N,N'-bis[(pyridin-4-yl)methylidene]hydrazine.

The hydrothermal synthesis of the novel complex poly[aqua(μ4-benzene-1,2,3-tricarboxylato)[μ2-4,4'-(hydrazine-1,2-diylidenedimethanylylidene)dipyridine](μ3-hydroxido)dizinc(II)], [Zn(C9H3O6)(OH)(C12H10N4)(H2O)]n, is described. The benzene-1,2,3-tricarboxylate ligand connects neighbouring Zn4(OH)2 secondary building units (SBUs) producing an infinite one-dimensional chain. Adjacent one-dimensional chains are connected by the N,N'-bis[(pyridin-4-yl)methylidene]hydrazine ligand, forming a two-dimensional layered structure. Adjacent layers are stacked to generate a three-dimensional supramolecular architecture via O-H...O hydrogen-bond interactions. The thermal stability of this complex is described and the complex also appears to have potential for application as a luminescent material.

Mechanochemical Preparation of Cobalt Nanoparticles through a Novel Intramolecular Reaction in Cobalt(II) Complexes

A novel solid state reaction involving a series of cobalt(II) hydrazine‐azides has been used to prepare metallic cobalt nanoparticles. The reactions of [Co(N2H4)(N3)2], [Co(N2H4)2(N3)2], and [Co(N2H4)(N3)Cl]·H2O via NaOH, KOH as reactants were carried out in the solid state. These complexes undergo an intramolecular two‐electron oxidation‐reduction reaction at room temperature, producing metallic cobalt nanoparticles (Co1–Co6). The aforementioned complexes contain cobalt(II) that is an oxidizing agent and also hydrazine ligand as a reducing agent. Other products produced include sodium azide and ammonia gas. The cobalt metal nanoparticles were characterized using X‐ray powder diffraction (XRD), scanning electron microscopy (SEM), and vibrating sample magnetometer (VSM). The synthesized cobalt nanoparticles have similar morphologies; however, their particle size distributions are different.

Synthesis and structure of zinc dichloride bis(t-butylhydrazine) monohydrate

AbstractZnCl

The preparation of nickel nanoparticles through a novel solid-state intramolecular reaction of polynuclear nickel(II) complex

A novel solid-state reaction involving [Ni6(N2H4)6(SO4)4(OH)2(H2O)8](SO4)(H2O)10 has been used to prepare nickel nanoparticles. The reaction of [Ni6(N2H4)6(SO4)4(OH)2(H2O)8](SO4)(H2O)10 via NaOH, KOH, and/or Na2CO3 as a reactant was carried out in the solid state. The complex undergoes an intramolecular two-electron oxidation–reduction reaction at room temperature, producing metallic nickel nanoparticles (Ni1, Ni2 and Ni3). The aforementioned complex contains nickel(II) that is an oxidizing agent and also hydrazine ligand as a reducing agent. Other products produced include sodium azide and ammonia gas. The nickel metal nanoparticles were characterized using X-ray powder diffraction, scanning electron microscopy, and vibrating sample magnetometer. The synthesized nickel nanoparticles have similar morphologies; however, their particle size distributions are different.

Unique Y-shaped lanthanide aggregates and single-molecule magnet behaviour for the Dy4analogue

The assembly of N'-(amino-(pyrimidin-2-yl)methylene)-o-vanilloyl hydrazine ligands (H2L, Scheme 1) with different lanthanide perchlorates produces novel Y-shaped tetranuclear complexes, [Ln4(μ3-OH)(L(2-))4(H2O)6]·(ClO4)3·6H2O, where Ln = Tb (1), Dy (2) and Ho (3). The formation of this unprecedented Y-shaped topology is largely ascribed to the versatility of the mixed-donor hydrazone ligands in terms of their potential denticity. Analysis of the susceptibility data shows that only the Dy-based molecule features SMM-like behaviour. The synthetic methodology of employing H2L and related ligands has provided a very promising route towards new families of magnetic coordination clusters with novel metal topologies and properties.

3D Energetic Metal–Organic Frameworks: Synthesis and Properties of High Energy Materials

Metal–organic frameworks (MOFs) have attracted great attention because of their intriguing molecular topologies and potential applications in chemical separation, gas storage, drug delivery, catalysis and chemical sensor technology. Particularly, MOFs could also be potential energetic materials because of their high densities and high heats of detonation. For example, Hope-Weeks and co-workers recently reported two hydrazine-perchlorate 1D MOFs [(Ni(NH2NH2)5(ClO4)2)n (NHP), and (Co(NH2NH2)5(ClO4)2)n (CHP)] with linear polymeric structures, which were regarded as possibly the most powerful metal-based energetic materials known to date, with heats of detonation comparable with that of hexanitrohexaazaisowutzitane (CL-20; about 1.5 kcalg ). Unfortunately, these coordination polymers were highly sensitive to impact deriving from their low rigidity characteristic of such linear polymeric structures, which makes practical use infeasible. In order to decrease the sensitivities, the same authors also used a hydrazine derivative (hydrazine-carboxylate) as the ligand to construct MOFs with 2D sheet structures [((Co2(N2H4)4(N2H3CO2)2)(ClO4)2·H2O)n (CHHP) and ((Zn2(N2H4)3(N2H3CO2)2)(ClO4)2·H2O)n (ZnHHP)], which showed a considerable reduction to the sensitivity, however, concomitantly their heats of detonation decreased (Figure 1). Despite these advances, current coordination frameworks are only limited to be a 1D or 2D structure. Compared with 1D linear and 2D layered structures, three-dimensional (3D) frameworks possess more complicated connection modes, which could further enhance structural reinforcement, hence improve the stabilities and energetic properties. A lot of 3D MOFs have been synthesized with interesting magnetic, catalytic, and luminescent properties, some of them incorporate a variety of energetic moities such as nitrate anions (NO3 ), perchlorate anions (ClO4 ) into the 3D frameworks. However, their potential applications as energetic materials have not been disclosed or discussed; relevant data about energetic properties are also missing in the literature. Additionally, both reported 1D and 2D energetic MOFs based on the perchlorate anions, have been scrutinized by the US Environmental Protection Agency (EPA) because they promote thyroid dysfunction and are teratogenic. Continuing our interest in finding new highly energetic, eco-friendly energetic materials, we explore the preparation of halogen-free energetic 3D MOFs, for which two polymers [Cu(atrz)3(NO3)2]n (1) and [Ag(atrz)1.5(NO3)]n (2) were designed by replacing the hydrazine ligand with 4,4’-azo1,2,4-triazole (atrz). Here, we chose to use atrz as a ligand for the following reasons: 1) as a nitrogen-rich heterocyclic backbone, atrz possesses a high nitrogen content (N%= Figure 1. Energetic MOFs with different topologies.

Tetranuclear Lanthanide (III) Complexes Containing Dimeric Subunits: Single-Molecule Magnet Behavior for the Dy4 Analogue

The reaction of the lanthanide(III) salts [Dy(III), Tb(III), and Gd (III)] with a hetero donor chelating ligand N'-(2-hydroxy-3-methoxybenzylidene)-6-(hydroxymethyl) picolinohydrazide (LH3) and pivalic acid (PivH) in the presence of tetra-n-butylammonium hydroxide (TBAH) afforded the tetranuclear Ln(III) coordination compounds, [Ln4(LH)2(LH2)2(μ2-η(1)η(1)Piv)2(η(1)Piv)4]·2CHCl3 [Ln = Dy(1), Tb(2), and Gd(3)]. The molecular structure of these complexes reveals that the tetranuclear derivatives are composed of two dinuclear subunits which are interconnected through the coordination action of the picolinoyl hydrazine ligand. Within each subunit two different types of Ln(III) ions are present. One of these is eight-coordinate in a distorted triangular dodecahedral geometry while the other is nine-coordinate in a distorted spherical capped square antiprism geometry. Alternating current (ac) susceptibility measurements of complex 1 reveal a frequency- and temperature-dependent two step out-of-phase signals under 1kOe DC field which is characteristic of a single-molecule magnet (SMM) behavior. Analysis of the magnetic data afforded the anisotropic barriers and relaxation times: Δ/kB = 62.6 K, τ0 = 8.7 × 10(-7) s; Δ/kB = 26.3 K, τ0 = 1.26 × 10(-6) s for the slow and fast relaxations respectively.

Bis[μ-1-(3,5-dichloropyridin-2-yl)-2-(pyridin-3-ylmethylidene)hydrazine]bis[(nitrato-κO)silver(I)] acetonitrile disolvate

In the centrosymmetric binuclear title complex, [Ag2(NO3)2(C11H8Cl2N4)2]·2CH3CN, the AgI atom is four-coordinated and exhibits a highly distorted tetrahedral coordination sphere defined by three N atoms from two 1-(3,5-di­chloro­pyridin-2-yl)-2-(pyridin-3-yl­methyl­idene)hy­drazine ligands and one O atom from a nitrate anion. Inter­molecular N—H⋯O hydrogen bonds link the complex mol­ecules, resulting in a two-dimensional supra­molecular structure parallel to (001).

Synthesis, thermal and infrared spectroscopic studies of hydrazinated mixed metal fumarates

A series of hydrazinated complexes of mixed nickel manganese zinc ferrous fumarates were synthesized from aqueous metal chlorides solution and sodium fumarate–hydrazine hydrate mixture. These complexes were characterized by chemical analysis, infrared spectroscopy, thermogravimetry-differential scanning calorimetry and isothermal mass loss studies. The hydrazine ligand in these complexes shows bidentate bridging nature while, carboxylate ion displays monodentate behaviour. Thermal decomposition studies indicate 3-step decomposition, involving 2-step dehydrazination and 1-step decarboxylation. The thermal decomposition residues were characterized by X-ray diffractometry, transmission electron microscopy and infrared spectroscopy.

Synthesis, thermo-analytical and IR spectral studies of hydrazinated mixed metal carboxylates: A single source precursor to nanosize mixed metal oxides

A series of hydrazinated mixed nickel manganese zinc ferrous hydrazine fumarate complexes were synthesized from aqueous mixed metal chloride solutions and sodium fumarate-hydrazine hydrate mixture. The detailed characterization was carried out by chemical analysis, infrared spectroscopy and isothermal mass loss studies. The hydrazine ligand in these complexes shows bidentate bridging nature while fumarate anion exhibit monodentate behavior. These complexes act as single source precursors for nanosize ferrites. Thermal decomposition of these precursors was studied upto 800°C in static air using simultaneous TG/DTA. The thermal decomposition study indicates 3-step decomposition of these precursors into nanosize mixed metal oxides. The nanosize mixed metal oxides were then characterized by X-ray diffraction, transmission electron microscopy and infrared spectral studies.

Synthesis, Crystal Structures, and Antifungal Activities of N’-3,5-Dichloro-2-hydroxybenzylidene)-2-hydroxy-3-methylbenzohydrazide and its Oxovanadium(V) Complex [N’-(3,5-Dichloro-2-oxidobenzylidene-κO)-2-hydroxy-3-methylbenzohydrazidato-κ 2 N’,O](methanol-κO)(methanolato-κO)oxidovanadium(V)

A new hydrazine ligand, N’-3,5-dichloro-2-hydroxybenzy lidene)-2-hydroxy-3-methylbenzohydrazide, and its oxovanadium(V) complex, [N’-(3,5-dichloro-2-oxidobenzylidene-κO)-2-hydroxy-3-methylbenzohydrazidato-κ 2 N’,O](methanol-κO) (methanolato-κO)oxidovanadium(V), were prepared and were structurally characterized by elemental analysis, infrared (IR) spectra, and single-crystal x-ray diffraction. The hydrazine ligand coordinates to the V atom through the phenolic O, imino N, and ethanolic O atoms. The V atom in the complex is in an octahedral coordination, with the three donor atoms of the hydrazine ligand and one methanolato O atom defining the equatorial plane, and with one methanol O atom and one oxo O atom occupying the axial positions. The displacement of the V atom from the equatorial plane toward the axial oxo O atom is 0.308(2) Å. The hydrazine ligand and the complex showed moderate to strong antifungal activities against the fungi Aspergillus flavus, Fusarium, and Candida albicans.

Synthesis and Crystal Structures of N′-3,5-Dibromo-2-Hydroxybenzylidene)-2-Hydroxy-3-Methylbenzohydrazide and its Oxovanadium(V) Complex [N′-(3,5-Dibromo-2-Oxidobenzylidene-κO)-2-Hydroxy-3-Methylbenzohydrazidato-κ 2 N′,O](Methanol-κO)(Methanolato-κO)Oxidovanadium(V)

A new hydrazine ligand N′-3,5-dibromo-2-hydroxybenzylidene)-2-hydroxy-3-methylbenzohydrazide (1) and its oxovanadium(V) complex [N′-(3,5-dibromo-2-oxidobenzylidene-κO)-2-hydroxy-3-methylbenzohydrazidato-κ 2 N′,O](methanol-κO)(methanolato-κO)oxidovanadium(V) (2), were prepared and were structurally characterized by elemental analysis, IR spectra and single-crystal X-ray diffraction. Compound 1 crystallizes in the triclinic space group P−1, with unit cell dimensions a = 7.813(2) A, b = 8.748(2), c = 26.071(6) A, α = 85.763(2)°, β = 81.521(2)°, γ = 89.358(3)°, V = 1757.6(7) A3, Z = 4, R 1 = 0.0587, and wR 2 = 0.1054. Compound 2 crystallizes in the triclinic space group P-1, with unit cell dimensions a = 7.777(3) A, b = 11.594(3), c = 12.363(3) A, α = 107.965(3)°, β = 103.190(2)°, γ = 96.656(2)°, V = 1011.3(5) A3, Z = 2, R 1 = 0.0634, and wR 2 = 0.1480. The hydrazine ligand coordinates to the V atom through the phenolic O, imino N, and ethanolic O atoms. The V atom in the complex is in an octahedral coordination, with the three donor atoms of the hydrazine ligand and one methanolato O atom defining the equatorial plane, and with one methanol O and one oxo O atoms occupying the axial positions. The displacement of the V atom from the equatorial plane towards the axial oxo O atom is 0.305(2) A. A new hydrazine ligand N′-3,5-dibromo-2-hydroxybenzylidene)-2-hydroxy-3-methylbenzohydrazide and its oxovanadium(V) complex are presented.

New dimeric and supramolecular organotin(IV) complexes with a tridentate schiff base as potential biocidal agents

The paper describes the synthesis and structural characterization of six new diorganotin(IV) compounds 1–6, [R 2SnL] and a monoorganotin(IV) derivative, C 4H 9SnClL (7). Here L = N′-(5-bromo-2-oxidobenzylidene)-N-(oxidomethylene)hydrazine ligand with ONO tridentate chelation capability and R = CH 3 ( 1), C 2H 5 ( 2), n-C 4H 9 ( 3), C 6H 5 ( 4), C 8H 17 ( 5), tert-C 4H 9 ( 6), The packing diagram offers a supramolecular structure for 1 and a dimeric structure for 4 with distorted square-pyramidal and distorted trigonal geometry, respectively. The different geometry of 1 than 4 can be attributed to the presence of intermolecular non-covalent Sn---O and Sn---H interactions in the former. The antifungal, antibacterial, antiurease and antileishmanial activities of these complexes proved them to be active biologically and may be formulated as new metal-based drugs in future.

A new hydrazine-bridged thioantimonate Mn2Sb4S8(N2H4)2: Synthesis, structure, optical and magnetic properties

Abstract A new thioantimonate [Mn 2 Sb 4 S 8 (N 2 H 4 ) 2 ] ( 1 ) was solvothermally synthesized by reacting Mn and Sb 2 S 3 with S in hydrazine monohydrate solution. The single crystal structure analysis revealed that all Mn sites adopt distorted octahedral shapes and all Sb sites have either four-fold coordinated SbS 4 configurations or square pyramidal SbS 5 geometry. These polyhedra units are interconnected into two-dimensional layers via the sharing S atoms. These layers are further bridged into a novel three-dimensional framework by intra- and inter-layer hydrazine ligands. The compound 1 is a semiconductor with a band gap of 1.59 eV and displays paramagnetic behavior at high temperature and switches to antiferromagnetic ordering at 40 K.

A novel 3D cadmium coordination polymer constructed from hydrazine and benzene-1,2,4,5-tetracarboxylic acid: Synthesis, structure and fluorescent property

Abstract A novel three-dimensional (3D) coordination polymer [Cd(bta)0.5(N2H4)(H2O)]·H2O (1) (H4bta = benzene-1,2,4,5-tetracarboxylic acid; N2H4 = hydrazine) was synthesized hydrothermally and characterized by IR, elemental analysis, TGA and X-ray diffraction analysis. Compound 1 is the first example of 3D coordination compound containing trans-μ2-bridging ligand N2H4. In 1, Cadmium atoms are coordinated by bta4− ligands to form sinusoidal ruffling layers and the layer are further linked by hydrazine ligands into 3D network with a (83)(85·10) topology structure. In addition, the thermogravimetric analysis and fluorescent property of compound 1 have been investigated.

Bis(N′-benzoylpyridine-4-carbohydrazide)(1,10-phenanthroline)copper(II) dinitrate

In the title complex, [Cu(C13H11N3O2)2(C12H8N2)](NO3)2, the CuII atom (site symmetry 2) is coordinated by four N atoms from one 1,10-phenanthroline and two hydrazine ligands, respectively. The hydrazine ligands coordinate to the CuIIatom by a pyridine N atom. These four atoms form a slightly distorted square-planar N4 donor set. In the packing, two additional Cu⋯O inter­actions occur [Cu⋯O = 2.462 (2) Å], resulting in a typical Jahn–Teller-distorted octahedral environment around the Cu atom. N—H⋯O hydrogen bonds result in a three-dimensional network. The O atoms of the anion are disordered over two positions in a 0.68 (2):0.32 (2) ratio.

Hydrazine-hydrothermal method to synthesize three-dimensional chalcogenide framework for photocatalytic hydrogen generation

A novel chalcogenide, [Mn 2Sb 2S 5(N 2H 4) 3] (1), has been synthesized by the hydrazine-hydrothermal method. X-ray crystallography study reveals that the new compound 1 crystallizes in space group P1̄ (no. 2) of the triclinic system. The structure features an open neutral three-dimensional framework, where two-dimensional mesh-like inorganic layers are bridged by intra- and inter-layer hydrazine ligands. Both two Mn1 and Mn2 sites adopt distorted octahedral coordination. While two Sb1 and Sb2 sites exhibit two different coordination geometries, the Sb1 site is coordinated with three S atoms to generate a SbS 3 trigonal-pyramidal geometry, and the Sb2 site adopts a SbS 4 trigonal bipyramidal coordination geometry. It has an optical band gap of about ∼2.09 eV, which was deduced from the diffuse reflectance spectrum, and displays photocatalytic behaviors under visible light irradiation. Magnetic susceptibility measurements show compound 1 obeys the Curie–Weiss law in the range of 50–300 K.

Poly(vinylbenzylchloride) beads grafted with polymer brushes carrying hydrazine ligand for reversible enzyme immobilization

AbstractPoly(glycidylmethacrylate), p(GMA), brush grafted poly(vinylbenzyl chloride/ethyleneglycol dimethacrylate), p(VBC/EGDMA), beads were prepared by suspension polymerization and the beads were grafted with poly(glycidyl methacrylate), p(GMA), via surface‐initiated atom transfer radical polymerization aiming to construct a material surface with fibrous polymer. The epoxy groups of the fibrous polymer were reacted with hydrazine (HDZ) to create affinity binding site on the support for adsorption of protein. The influence of pH, and initial invertase concentration on the immobilization capacity of the p(VBC/EGDMA‐g‐GMA)‐HDZ beads has been investigated. Maximum invertase immobilization onto hydrazine functionalized beads was found to be 86.7 mg/g at pH 4.0. The experimental equilibrium data obtained invertase adsorption onto p(VBC/EGDMA‐g‐GMA)‐HDZ affinity beads fitted well to the Langmuir isotherm model. It was shown that the relative activity of immobilized invertase was higher than that of the free enzyme over broader pH and temperature ranges. The Km and Vmax values of the immobilized invertase were larger than those of the free enzyme. After inactivation of enzyme, p(VBC/EGDMA‐g‐GMA)‐HDZ beads can be easily regenerated and reloaded with the enzyme for repeated use. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009

Use of Hydrazine in the Hydrothermal Synthesis of Chalcogenides: the Neutral Framework Material [Mn2SnS4(N2H4)2

The reaction system Mn/Sn/S/hydrazine/water at approximately 150 degrees C afforded [Mn(2)SnS(4)(N(2)H(4))(2)] (1). The compound has a unique neutral three-dimensional framework with bridging hydrazine ligands and a variety of interconnectivity modes between MnL(6) (L = N, S) octahedra. The complex structure of 1 leads to strong antiferromagnetic interactions between the Mn(2+) centers and ordering at approximately 41 K. The stabilization of 1 underscores the high potential of hydrazine to promote the formation of novel chalcogenide materials under solvothermal conditions.

Structure and chemical properties of a copper(II) hydrazido complex: [{Cu(HB(3,5-iPr2pz)3)}2(μ-NCOOEt)2

The novel copper(II) hydrazido(2−) complex ligated by hydrotris(pyrazolyl)borate was synthesized to obtain insight into the copper coordination chemistry in the presence of diazene and hydrazine ligands. The structure of [{Cu(L1)}2(μ-NCOOEt)2] was determined by X-ray crystallography, where L1=hydrotris(3,5-diisopropyl-1-pyrazolyl)borate anion, and along with spectroscopic characterization, e.g. UV–Vis and ESR, prove the presence of copper(II) centers.