Sonochemical synthesis and characterization of three nano zinc(II) coordination polymers; Precursors for preparation of zinc(II) oxide nanoparticles

Nanostructures of three Zinc(II) coordination polymers, [Zn(NNO)₂(H₂O)₄]_n (1), [Zn(PNNO)₂(H₂O)₂]_n (2) and [Zn(H₂O)₆]·(INNO)₂ (3) {NNO: Nicotinic acid N-oxide, PNNO: Picolinic acid N-oxide and INNO: Isonicotinic acid N-oxide}, have been synthesized by a sonochemical process and reaction of ligands with Zn(CH₃COO)₂. The Zinc(II) oxide nano-particles have been synthesized from thermolysis of [Zn(NNO)₂(H₂O)₄]_n (1), [Zn(PNNO)₂(H₂O)₂]_n (2) and [Zn(H₂O)₆]·(INNO)₂ (3) at two different methods (with surfactant and without surfactant) and two temperatures (200 and 600 °C). The ZnO nanoparticles were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). Comparison of the SEM images of ZnO nano-particles at two different methods and temperatures shows that higher temperature results in an increasing of agglomeration and thus small and spherical ZnO particles with good separation were produced by thermolysis of compounds at 200 °C and by use of surfactant.     

Sonochemical syntheses of a new nano-plate cadmium(II) coordination polymer as a precursor for the synthesis of cadmium(II) oxide nanoparticles

Nanoplates of the three-dimensional coordination polymer, {[Cd(3)(3-pyc)(4)(N(3))(2)(H(2)O)](n) (1), 3-pyc(-)=pyridine-3-carboxylate), have been synthesized by a sonochemical process and characterized by scanning electron microscopy, X-ray powder diffraction, IR spectroscopy and elemental analyses. Cadmium(II) oxide nanoparticles were prepared from thermal decomposition in oleic acid and direct calcination of compound 1 at different temperatures. The thermal stability of nano-sized compound 1 was studied by thermal gravimetric (TG) and differential thermal analyses (DTA). Results show that the size and morphology of the CdO nanoparticles are dependent upon the particles size of compound 1 and the thermolysis temperature. A decrease in the particle size of compound 1 leads to a decrease in the particle size of the CdO, while an increase in the processing temperature leads to an increase in the particle size of the produced cadmium(II) oxide nano-particles.     

Sonochemical synthesis and characterization of new one-dimensional manganese(II) coordination polymer nanostructures

A new Mn(II) coordination polymer, [Mn (L₁)₂(NCS)₂]_n (1) [L₁ = 3,4-bis(4-pyridyl)-5-(2-pyridyl)-1,2,4-triazole] was synthesized by the reaction of ligand L₁ and mixtures of manganese(II) acetate and potassium thiocyanate using the heat gradient method. Compound 1 has been characterized by IR spectroscopy, elemental analyses and X-ray crystallography. The crystal structure of compound 1 was determined by single-crystal X-ray diffraction and shows a new interesting one-dimensional coordination polymer. Nanostructures of compound 1 have been synthesized by sonochemical method. The products were characterized by X-ray powder diffraction, scanning electron microscopy (SEM), and IR spectroscopy. The thermal stability of nano particles of compound 1 was studied by thermal gravimetric and differential thermal analyses.     

Sonochemical synthesis and characterization of nano-sized lead(II) 3D coordination polymer: Precursor for the synthesis of lead(II) oxybromide nanoparticles

Nanoparticles of a three-dimensional coordination polymer, [Pb(L)(μ₂-Br)(H₂O)]_n (1), (L^? = 1H-1,2,4-triazole-3-carboxylate), have been synthesized by an ultrasonic method and characterized by scanning electron microscopy, X-ray powder diffraction, IR spectroscopy and elemental analyses. The thermal stability of compound 1 both its bulk and nano-size has been studied by thermal gravimetric (TG) and differential thermal (DTA) analyses and compared each other. Concentration of initial reagents effects and the role of power ultrasound irradiation on size and morphology of nano-structured compound 1, have been studied. Calcination of the compound 1 at 500 °C under air atmosphere yields Pb₃O₂Br₂ nanoparticles.     

Sonochemical syntheses of a nanoparticles cadmium(II) supramolecule as a precursor for the synthesis of cadmium(II) oxide nanoparticles

Nanoparticles of a three-dimensional supramolecular Cd(II) compound, [Cd(L)(2)(H(2)O)(2)] (1), (L(-)=1H-1,2,4-triazole-3-carboxylate), have been synthesized by a sonochemical process and characterized by scanning electron microscopy, X-ray powder diffraction, IR spectroscopy and elemental analyses. The thermal stability of compound 1 in both its bulk and nano-size has been studied by thermal gravimetric (TG) and differential thermal analyses (DTA) and compared with each other. Concentration of initial reagents effects on size and morphology of nano-structured compound 1, have been studied. Calcination of the single crystals and nano-sized compound 1 at 650°C under air atmosphere yields CdO nanoparticles.     

Sonochemical synthesis of two new nano structure zinc(II) 1,10-phenanthroline coordination supramolecular compounds: New precursors to produce nano-sized zinc(II) oxide

Nanoparticles of two zinc(II) coordination supramolecule compounds (CSCs), [Zn(L)Cl2] (1) and [Zn(L)Br2] (2) L = 1,10-phen = 1,10-phenanthroline ligand, have been synthesized by use of a sonochemical process and characterized by scanning electron microscopy (SEM), X-ray powder diffraction (XRPD), Fourier transform infrared (FTIR) spectroscopy and elemental analyses. The single crystal X-ray data of compounds 1 and 2 imply that the Zn⁺² ions are four coordinated. Topological analysis shows that the compound 1 and 2 are new topology for net: 1,3M4-1. Nanoparticles of zinc(II) oxide have been prepared by calcination of two different zinc(II) CPs at 500 °C that were characterized by scanning electron microscopy (SEM), X-ray powder diffraction (XRD) and IR spectroscopy.     

Sonochemical syntheses of a nano-sized copper(II) supramolecule as a precursor for the synthesis of copper(II) oxide nanoparticles

Nanoparticles of a three-dimensional supramolecular, [Cu(L)₂(H₂O)₂] (1), (L⁻ = 1H-1,2,4-triazole-3-carboxylate), have been synthesized by a sonochemical process and characterized by scanning electron microscopy, X-ray powder diffraction, IR spectroscopy and elemental analyses. The thermal stability of compound 1 both its bulk and nano-size has been studied by thermal gravimetric (TG) and differential thermal analyses (DTA) and compared each other. Concentration of initial reagents effects on size and morphology of nano-structured compound 1, have been studied. Calcination of the nano-sized compound 1 at 600 °C under air atmosphere yields CuO nanoparticles.     

Synthesis of a new Hg(II) coordination polymer: Ultrasonic-assisted synthesis and mechanical preparation of nanostructure

A new mercury(II) coordination polymer, [Hg(4-bpmo)I₂]_n (1), (4-bpmo = N,N′-bis(pyridin-4-ylmethyl)oxalamide), was synthesized, by branched tube method, and structurally characterized by single-crystal X-ray diffraction. Compound 1 is a polymer with a distorted tetrahedral HgN₂I₂ coordination environment. The thermal stability of 1 was studied by thermal gravimetric (TG) and differential thermal (DTA) analyses. Also 1 was prepared by a sonochemical process at ambient temperature. Reaction time and concentration of initial reagents effects on the size and morphology were studied. Nanoparticles of 1, was synthesized easily by a mechanical method (neat grinding). The resulting structures were characterized by scanning electron microscopy (SEM), IR spectroscopy and X-ray powder diffraction (XRD).     

Sonochemical syntheses of binuclear lead(II)-azido supramolecule with ligand 3,4,7,8-tetramethyl-1,10-phenanthroline as precursor for preparation of lead(II) oxide nanoparticles

The new neutral binuclear lead(II) azido coordination compound, [Pb₂(tmph)₂(μ-N₃)₂(CH₃COO)₂] (1) [tmph = 3,4,7,8-tetramethyl-1,10-phenanthroline], has been synthesized by a sonochemical method. Single crystal X-ray structure shows that the overall structure of 1 is binuclear unit. Complex 1 has a bridging azido pathway, end-to-end bridging azides between a pair of lead(II) centers. This is further extended into a one-dimensional (1D) and three-dimensional (3D) supramolecular structure by Pb⋯C and π–π weak directional intermolecular interactions. The coordination number of lead(II) ions is seven, PbN₄O₃, with two N-donor atoms from tmph ligands and three O-donors from acetate anions and two N-donors from two azide anions. It has a “stereo-chemically active” electron lone pair, and the coordination sphere is hemidirected. The PbO nanoparticles were obtained by thermolysis of 1 at 180 °C with oleic acid as a surfactant. The morphology and size of the prepared PbO samples were further observed using scanning electron microscopy (SEM).     

Sonochemical synthesis of nanoscale mixed-ligands lead(II) coordination polymers as precursors for preparation of Pb2(SO4)O and PbO nanoparticles; thermal,structural and X-ray powder diffraction studies

Nano-structures of two new Pb(II) two-dimensional coordination polymers, [Pb(μ-4-pyc)(μ-NCS)(μ-H₂O)]_n (1) and [Pb(μ-4-pyc)(μ-N₃)(μ-H₂O)]_n (2), 4-Hpyc = 4-pyridinecarboxylic acid were synthesized by a sonochemical method. The new nano-structures were characterized by scanning electron microscopy, X-ray powder diffraction, IR spectroscopy and elemental analyses. Compounds 1 and 2 were structurally characterized by single crystal X-ray diffraction and consist of two-dimensional polymeric units. The thermal stability of compounds 1 and 2 were studied by thermal gravimetric and differential thermal analyses and compared. Pb₂(SO₄)O and PbO nanoparticles were obtained by calcination of the nano-structures of compounds 1 and 2 at 600 °C, respectively.     

Sonochemical synthesis and structural characterization of a new nanostructured Co(II) supramolecular coordination polymer with Lewis base sites as a new catalyst for Knoevenagel condensation

A new Co(II) mixed-ligand coordination supramolecular polymer with composition [Co₂(ppda)(4-bpdh)₂(NO₃)₂]_n (1) (where, ppda = p-phenylenediacrylic acid, 4-bpdh = 2,5-bis(4-pyridyl)-3,4-diaza-2,4-hexadiene) was synthesized using solvothermal, mechanochemical and sonochemical methods. Compound 1 and the new nanostructure have been characterized by single-crystal X-ray, infrared spectroscopy (IR), powder X-ray diffraction (PXRD) analysis and scanning electron microscopy (SEM). The thermal stability of compound 1 was also studied by thermal gravimetric analysis (TGA). The surface area of these compounds was determined by BET. The single-crystal X-ray data shows a new interesting two-dimensional coordination polymer (CP). In addition, the effect of various sonication concentrations of initial reagents, power of ultrasound irradiation and also the time on the size and morphology of nano-structured coordination polymer 1 were evaluated. Moreover, it has been demonstrated that the nanostructure of the CP1 can be used as a catalyst in Knoevenagel condensation reaction.     

Sonochemical preparation of pure t-LaVO4 nanoparticles with the aid of tris(acetylacetonato)lanthanum hydrate as a novel precursor

Herein a simple and fast method is introduced for the synthesis of lanthanum orthovanadate (LaVO₄) nanoparticles under ultrasound irradiation. The effect of tris(acetylacetonato)lanthanum hydrate ([La(acac)₃·3H₂O]) and La(OAc)₃ as two different precursors on the morphology and phase purity of LaVO₄ was investigated. To optimum the particle size of the products, sonication time and the kind of surfactants have been changed. The as-synthesized products were characterized by XRD, FT-IR, SEM, TEM, and EDS. Based on the obtained results, it was found that the size and shape of the sonochemically formed LaVO₄ nanoparticles were dramatically dependent on the sonication time, type of surfactant and lanthanum precursor. According to the XRD results, it was observed that pure tetragonal phase lanthanum orthovanadate (t-LaVO₄) could be obtained only by using [La(acac)₃·3H₂O] as precursor under ultrasound irradiation for 30 min. On the other hand, monoclinic phase lanthanum orthovanadate (m-LaVO₄) with poor crystallinity has been produced by vigorous stirring at room temperature without sonication.     

Sonochemical synthesis of nano-scale mixed-ligands lead(II) coordination polymers as precursors for preparation of PbO and PbBr(OH) nano-structures; thermal,structural and X-ray powder diffraction studies

Nano-structures of two new lead(II) two-dimensional coordination polymers, [Pb₂(2-pyc)₂(I)₂]_n (1) and [Pb₂(2-pyc)₂(Br)₂]_n (2), {2-Hpyc = 2-pyridinecarboxilic acid } were synthesized by a sonochemical method that produce the coordination polymers at nano-size. The new nano-structures were characterized by scanning electron microscopy, X-ray powder diffraction, IR spectroscopy and elemental analyses. Compounds 1 and 2 were structurally characterized by single crystal X-ray diffraction and consist of two-dimensional polymeric units. The thermal stability of compounds 1 and 2 were studied by thermal gravimetric and differential thermal analyses. PbO and PbBr(OH) nano-structures were obtained by calcination of the nano-structures of compounds 1 and 2 at 400 °C, respectively.     

Sonochemical syntheses and characterization of nano-sized lead(II) coordination polymer with ligand 1H-1,2,4-triazole-3-carboxylate

Nanoparticles of a two-dimensional coordination polymer, {[Pb(L)(μ_1,1-NCS)(H₂O)]}_n (1), (L⁻ = 1H-1,2,4-triazole-3-carboxylate), have been synthesized by a sonochemical process and characterized by scanning electron microscopy, X-ray powder diffraction, IR spectroscopy and elemental analyses. The thermal stability of compound 1 both its bulk and nano-size has been studied by thermal gravimetric (TG) and differential thermal (DTA) analyses and compared each other. Concentration of initial reagents effects and the role of power ultrasound irradiation on size and morphology of nano-structured compound 1, have been studied. Calcination of the single crystals and nano-sized compound 1 at 400 °C under air atmosphere yields mixture of PbS and Pb₂(SO₄)O nanoparticles. Results show that the size and morphology of the PbS and Pb₂(SO₄)O nanoparticles are dependent upon the particles size of compound 1. A decrease in the particles size of compound 1 leads to a decrease in the particles size of the PbS and Pb₂(SO₄)O.     

Sonochemical synthesis of two new nano lead(II) coordination polymers: Evaluation of structural transformation via mechanochemical approach

Two new lead(II) mixed-ligand coordination polymers, [Pb(PNO)(SCN)]_n (1) and [Pb(PNO)(N₃)]_n (2), (HPNO = picolinic acid N-oxide) were synthesized by a sonochemical method and characterized by scanning electron microscopy, X-ray powder diffraction, IR spectroscopy and elemental analysis. Compounds 1 and 2 were structurally characterized by single crystal X-ray diffraction. The thermal behavior of 1 and 2 were studied by thermal gravimetric analysis. Structural transformations of compounds 1 and 2 were evaluated through anion-replacement processes by mechanochemical method. Moreover, the effect of sonication conditions including time, concentrations of initial reagents and power of irradiation were evaluated on size and morphology of compounds 1 and 2.     

Sonochemical synthesis of a novel nanoscale 1D lead(II) [Pb2(L)2(I)4]n coordination Polymer,survey of temperature,reaction time parameters

One new lead(II) coordination supramolecular complex (CSC) (1D), [Pb₂(L)₂(I)₄]_n, L = C₄H₆N₂ (1-methyl imidazole), has been synthesized under different experimental conditions. Micrometric crystals (bulk) or nano-sized materials have been obtained depending on using the branch tube method or sonochemical irradiation. All materials have been characterized by scanning electron microscopy (SEM), powder X-ray diffraction (PXRD) and FT-IR spectroscopy. Single crystal X-ray analyses on complex 1 showed that Pb²⁺ ion is 4-coordinated. Topological analysis shows that the complex 1 is 2,3,5C2 net. Finally, the role of reaction time and temperature on the growth and final morphology of the structures obtained by sonochemical irradiation have been studied.     

Sonochemical synthesis of amorphous nanoscopic iron(III) oxide from Fe(acac)3

Amorphous nanoscopic iron(III) oxide with interesting magnetic properties was prepared by sonolysis of Fe(acac)(3) under Ar in tetraglyme with a small amount of added water. The organics content and the surface area of the Fe(2)O(3) nanoparticles can be controlled with an amount of water in the reaction mixture and it increases from 48 m(2)g(-1) for dry solvent up to 260 m(2)g(-1) when wet Ar is employed. For further monitoring of the particle size and morphology and for the study of the surface, magnetic and thermal properties, the sample with 2 vol.% of H(2)O was chosen. SEM showed nanoscopic composite particles of a uniform size distribution and nearly spherical shapes with an estimated diameter of 20 nm. Such composites are built from amorphous iron(III) oxide nanoparticles (3 nm) embedded in an acetate matrix as proved by TEM and IR spectroscopy. Temperature-dependent M?ssbauer spectra demonstrate a very narrow magnetic transition with an unusually low transition temperature around 25K reflecting the system of magnetically non-interacting ultrasmall particles with a narrow size distribution. The in-field (5T) M?ssbauer spectrum recorded at 5K shows a minimum change compared to the zero-field spectrum indicating an absence of the long-range magnetic ordering. The composite particles are thermally stable up to 150 degrees C, which is confirmed by DSC, TG, and by the constant surface area. At higher temperatures, acetate groups are removed from the particle surface, which is documented by the increased surface area and disappearance of their IR bands.     

Sonochemical synthesis of a new nano-sized barium coordination polymer and its application as a heterogeneous catalyst towards sono-synthesis of biodiesel

A new nano-sized barium coordination polymer, {(bipyH)[Ba₂(pydc)₂(Hpydc)(H₂O)₂]}_n·nH₂O (1), (bipy = 4,4′-bipyridine and H₂pydc = pyridine-2,6-dicarboxylic acid), has been sonochemically synthesized and fully characterized by scanning electron microscopy (SEM), X-ray powder diffraction (XRPD), FT-IR spectroscopy, thermogravimetric analysis (TGA) and elemental analyses. Compound 1 was structurally characterized by single crystal X-ray diffraction and it was shown that this compound consists of 1D anionic coordination polymers and bipyH⁺ cationic species that construct a three-dimensional supramolecular architecture via non-covalent interactions i.e. ion-pairing and hydrogen bonding. The role of compound 1 as a heterogeneous catalyst in the production of biodiesel was also investigated. A full conversion of soybean oil to biodiesel was accomplished in an exceptionally short timeframe through an ultrasonic-assisted transesterification process in the presence of compound 1.     

Sonochemical synthesis of two nanostructured silver(I) coordination polymers based on semi-rigid bis(benzimidazole) ligands

Nanoparticles of two silver(I) coordination polymers (CPs), [Ag₂(L1)₂(DCTP)]_n (1) and [Ag₂(L2)(DCTP)]_n (2) (L1 = 1,3-bis(5,6-dimethylbenzimidazol-1-ylmethyl)benzene, L2 = 1,4-bis(benzimidazol-1-yl)-2-butene, H₂DCTP = 2,5-dichloroterephthalic acid), were synthesized by the sonochemical approach and hydrothermal method. Both CPs were characterized by elemental analysis, IR spectra, single-crystal X-ray diffraction, scanning electron microscopy (SEM), and thermogravimetric analyses (TGA). CP 1 exhibits a 2D 4-connected sql net with the point symbol {4⁴.6²}. While CP 2 displays a 2D 3,4-connected 3,4L13 net with the point symbol {4.6²}₂{4².6².8²}. The structural diversity indicates that semi-rigid bis(benzimidazole) co-ligands play important roles in tuning the structures of the mixed Ag(I) CPs. The ultrasound irradiation time, temperature, and power showed significant effects on the morphology and growth process of the nanoparticles of two silver(I) CPs. The luminescence and photocatalytic properties of the nanoparticles of CPs 1–2 on the degradation of methyl blue (MB) were also investigated in detail.     

Synthesis of carboxyl superparamagnetic ultrasmall iron oxide (USPIO) nanoparticles by a novel flocculation-redispersion process

We report a novel flocculation-redispersion method to synthesize and purify the biocompatible superparamagnetic ultrasmall iron oxide (USPIO) nanoparticles coated with carboxyl dextran derivative. First, USPIO nanoparticles were synthesized and flocculated to form the large clusters through bridging effect of polyvinyl alcohol (PVA) during coprecipitation process. Then the flocculated USPIO was separated and purified from the solution conveniently through magnetic sedimentation. Finally, USPIO in the clusters were released again and well dispersed through electrostatic repelling effect of citric acid with the aid of ultrasonic. The dispersed carboxyl-functionalized USPIO was conjugated with the monoclonal antibodies. And it has been proved that the antibodies anchored on USPIO still retained their bioactivity after the conjugation. These results implied that the USPIO synthesized have good potential as active targeting molecular probe in biomedical application.