Sonochemical Synthesis and Characterization of A Nano-Rod Lead(II) Supramolecular, Three Dimensional Coordination Compound: New Precursor to Produce Pure Phase Nano-Sized Lead(II) Oxide

Nanorods of a lead(II) supramolecular three-dimensional (3D) coordination compound, [Pb(tfpb)₂]_n (1) (Htfpb?=?4,4,4-trifluoro-1-phenyl-1,3-butanedione), was prepared by the sonochemical method. The new nano-structure was characterized by scanning electron microscopy, X-ray powder diffraction, elemental analyses and IR spectroscopy. A single-crystal structure of the compound showed that the coordination number of Pb(II) is eight with six O-donor atoms from the tfpb ligand and two F-donors from anionic ligands. The 3D supramolecular structure of 1 is realized by weak directional C–F···F–C and π–π stacking interactions. After calcination of nano-sized 1 at 500?°C, pure phase nano-sized lead(II) oxide is produced.     

Fabrication of Silver Nanoparticles and 3D Interpenetrated Coordination Polymer Nanorods from the Same Initial Reagents

Nanorods of the three-dimensional coordination polymer, [Ag₂(μ ₂-py-4-c)₂] _n (1) [py-4-c⁻ = pyridine-4-carboxylate], have been synthesized by sonochemical process. The single-crystal X-ray data of compound 1 shows the formation of a 3D interpenetrated silver(I) coordination polymer, which has agostic interactions around the silver(I) ions and two types of Ag^I ions with O₂NAg1···O₂H, N₂ Ag2···O₂H₂ coordination spheres. Silver nanoparticles were fabricated from thermal decomposition of 1 nanorods. These nanostructures were characterized by X-ray powder diffraction (XRD) and scanning electron microscopy (SEM). The thermal stability of 1 was studied by thermo gravimetric (TG) and differential thermal (DT) analysis.     

Solvothermal Synthesis of a Nano-sized Aza-aromatic Base Adduct of a Cadmium(II) 4,4-Difluoro-1-phenyl-1,3-butandionate Coordination Compound

A new nano-structured cadmium(II) coordination compound, [Cd(phen)(dfpb)₂] (1) (phen?=?1,10-phenanthroline, dfpb?=?4,4-difluoro-1-phenyl-1,3-butandion), was synthesized by a solvothermal method and produced a coordination polymer in the nano-size range. The new nanostructure was characterized by scanning electron microscopy, X-ray powder diffraction elemental analysis and IR spectroscopy. Compound 1 was structurally characterised by single crystal X-ray diffraction. The single crystal structure shows a coordination number for the Cd ion of six with two N-donor atoms from the phen ligand and four O-donors from the two dfpb moieties. Self-assembly occurs by CH····F–C and π–π stacking interactions. The supramolecular features in these complexes are controlled by weak directional intermolecular interactions.     

Direct Synthesis of PbO Nanoparticles from a Lead(II) Nanoflower Coordination Polymer Precursor: Synthesis, Crystal Structure and DFT Calculations of [Pb(pcih)N3H2O] n with the Terminal Azide Unit

The first nanoflower lead(II) coordination compound, [Pb(pcih)N₃MeOH] _n (1), (“pcih” is the abbreviations of 2-pyridinecarbaldehyde isonicotinoylhy-drazoneate) were synthesized by a sonochemical method. The new nano-structure was characterized by transmission electron microscopy, scanning electron microscopy, X-ray powder diffraction, elemental analyses and IR spectroscopy. Single crystalline material was obtained using a heat gradient applied to a solution of the reagents. Compound 1 was structurally characterized by single crystal X-ray diffraction. The determination of the structure by single crystal X-ray crystallography showed that the complex taking the form of a zig-zag one dimensional polymer in the solid state and the coordination number of PbII ions is six, (PbN₄O₂), with three N-donor and one O-donor atoms from two “pcih” and one O-donors from methanol and one N atom from terminal azide anion. It has an asymmetrical coordination sphere. The supramolecular features in these complexes are guided and controlled by weak directional intermolecular interactions. The chains interact with each other through π–π stacking interactions creating a 3D framework. After thermolysis of 1 at 180 °C with oleic acid, pure phase nano-sized lead(II) oxide was produced. The morphology and size of the prepared PbO samples were further observed using SEM.     

Sonochemical Synthesis and Characterization of the New Micro-Hexagonal-Rod Lead (II)-Azido Coordination Compound

The preparation of micro hexagonal-rods of a new 1D polymeric lead(II) complex containing the Pb₂-(μ-N₃)₂ motif, [Pb(dmp)(N₃)₂] _n (dmp is the abbreviation of 2,9-dimethyl-1,10-phenanthroline) by the sonochemical method is described. The new microcrystal is characterized by scanning electron microscopy, X-ray diffraction (XRD), elemental analyses and infrared spectroscopy. A single crystalline material is obtained by applying a heat gradient applied to a solution of the reagents. The single-crystal XRD analyses show that the coordination number for the Pb(II) ions is six, PbN6, with “stereo-chemically active” electron lone pairs and the coordination sphere being hemidirected. The single-crystal X-ray data show the chains of [Pb(dmp)(N₃)₂] _n interact with each other through the π–π stacking interactions, which create a 3D framework.     

3D Supramolecular Polymer Constructed from Agostic, Polyhapto and Thallophillic Interactions: A New Precursor for Preparation of Tl2O3 Nanoflowers

A new thallium(I) supramolecular polymer, [Tl₄(μ₃-2,4-cfp)₄] _n (1) [2,4-Hcfp = 2-chloro-4-fluorophenol] (1) with disordered cubic cage structural unit has been synthesized and characterized. The single-crystal X-ray data of 1 shows four types of Tl^I ions in the tetranuclear cubic cage unit with a coordination number three. In addition to an intra-cage thallophillic interaction, an inter-cage thallophillic interaction also exists and results in formation of 1D supramolecular polymer. Short contacts, Tl···H and Tl···C, make 1 a 3D supramolecular polymer. Short Tl···F and Tl···Cl secondary interactions also exist. Finally the Tl-ions attain O₃Tl1···C₆Tl₂, O₃Tl2···TlClF, O₃Tl3···Tl₂ and O₃Tl4···C₂TlH coordination spheres with a stereochemically ‘active’ electron lone pair of electrons on the metal ions. The thermal stability of 1 was studied by thermogravimetric and differential thermal analyses. Nanostructures of thallium(III) oxide were prepared from calcination of fine powders of 1 at 570 and 630 °C. These nanostructures were characterized by X-ray powder diffraction and scanning electron microscopy .     

Sonochemical Synthesis of New Nano-Belt One-Dimensional Double-Chain Lead(II) Coordination Polymer; As Precursor for Preparation of PbBr(OH) Nano-Structure

Nano-structure of a new 1D double-chain Pb(II) coordination polymer, [Pb(μ-HPDC)(μ-Br)(H₂O)]_n (1), {H₂PDC = 2,3-pyrazinedicarboxylic acid} was synthesized by a sonochemical method. The new nano-structure was characterized by scanning electron microscopy, X-ray powder diffraction, IR spectroscopy and elemental analyses. The structure of compound 1 was determined by single crystal X-ray diffraction and consists of 1D double-chain polymeric units. The coordination number in compound 1 is six and each lead atom is coordinated by two oxygen atoms of HPDC⁻, two nitrogen atoms of HPDC⁻ ligands, one bromide atom and one oxygen of H₂O molecule. The thermal stability of compound 1 was studied by thermal gravimetric and differential thermal analyses. Calcination of the nano-belts of compound 1 at 500 °C under air atmospheres yielded nano-sized particles of PbBr(OH) that characterized by scanning electron microscopy and X-ray powder diffraction.     

Hydrothermal Synthesis of a Nano-sized Mercury(II) N–N–O Donor Coordination Compound

A novel nano-structures mercury(II) coordination compound, [Hg (HPCIH) I₂] (1), (“HPCIH” is the abbreviation of 2-pyridinecarbaldehyde isonicotinoyl hydrazone) has been synthesized by a hydrothermal method that produces the coordination compound at nano size. The new nanostructure was characterized by transmission electron microscopy, scanning electron microscopy, X-ray powder diffraction elemental analysis and IR spectroscopy. Compound 1 was structurally characterized by single crystal X-ray diffraction and the single-crystal structure of this complex shows that each mercury(II) center is five coordinated with two N-donor and one O-donor atoms from “HPCIH” ligand and two iodo anions. Self-assembly of this complexes is realized by CH····I, I····I and π–π stacking interactions. The supramolecular features in these complexes are controlled by weak directional intermolecular interactions.     

Direct Synthesis of CdO Nanoparticles from a Novel Nano-Rods Cadmium(II) 4,4-Difluoro-1-phenyl-1,3-butanedionate Nano Coordination Compound

A novel nano-rods cadmium(II) fluorine-substituted β-diketonate, [Cd(2,2′-bpy)(dfpb)₂] (1), (2,2′-bpy = 2,2′-bipyridine; dfpb = 4,4-difluoro-1-phenyl-1,3-butandion) has been synthesized by a sonochemical method that produces the coordination compound with nano dimensions. The new nanostructure was characterized by scanning electron microscopy, X-ray powder diffraction (XRD) elemental analysis and IR spectroscopy. Compound 1 was structurally characterized by single crystal X-ray diffraction. The single-crystal structure of this complex shows that the coordination number of the Cd^II ions is six with two N-donor atoms from the 2,2′-bpy ligand and four O-donors from two dfpb. Self-assembly of the complex occurs through CH···F–C and π–π stacking interactions. The supramolecular features of 1 are controlled by weak directional intermolecular interactions. CdO nanoparticles were obtained by thermolysis of 1 at 180 °C with oleic acid as a surfactant. The average diameter of the nanoparticles was estimated by the Scherrer equation to be 20 nm. The morphology and size of the CdO samples were further observed using SEM.     

Thermolysis Synthesis of Pure Phase Nano-Sized Cobalt(II) Oxide from Novel Cobalt(II)-Pyrazole Discrete Nano Coordination Compound

Nano-structures of a new discrete coordination compound of divalent cobalt with the pyrazol (pzH) containing the terminal isothiocyanate anions, [Co(pzH)₂(NCS)₂] (1), with discrete molecular architecture in solid state was synthesized by a sonochemical method. The new nanostructure was characterized by scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, X-ray powder diffraction, IR, and elemental analysis. The supramolecular features in these complexes are guided and controlled by weak directional intermolecular interactions. The discrete molecules interact with each other through labile interactions creating a 3D supramolecular framework. The CoO nanoparticles were obtained by thermolysis of 1 at 180 °C with oleic acid as a surfactant.     

Direct Synthesis of Cd3OSO4 Nano-particles From a New Three-dimensional Cadmium(II) Coordination Polymer Precursor

A new three-dimensional Cd(II) coordination polymer, {[Cd₃(3-pyc)₄(NCS)₂(H₂O)₄]·2H₂O} _n (1); 3-Hpyc = 3-pyridinecarboxylic acid, was prepared and characterized by elemental analyses and IR spectroscopy. Compound 1 was structurally characterized by single-crystal X-ray diffraction. The structural determination shows that the compound is a new 3D coordination polymer has different environments containing CdO₅NS and CdO₂N₄ units. This polymeric precursor has been used in the preparation of Cd₃OSO₄ nanoparticles by thermolysis in oleic acid. The new nano-structure of Cd₃OSO₄ was characterized by scanning electron microscopy and X-ray powder diffraction. This study demonstrates that coordination polymers may be suitable precursors to the preparation of desirable nanoscale materials.     

Assembly,Fluorescent and Adsorption Properties of Two Cadmium(II)/Cobalt(II) Coordination Complexes Functionalized by the Flexible Bis(Pyridyl)-bis(Amide) Ligand

A new cadmium(II) and a new cobalt(II) coordination complexes [Cd₅(BTB)₄(HL)₂]·2H₂O (1) and [Co(HBTB)(L)]·2H₂O (2) [H₃BTB?=?1,3,5-tri(4-carboxylphenyl)benzene, L?=?N,N′-bis(3-pyridyl)octandiamide] were prepared under the solvothermal conditions by the assembly of cadmium(II)/cobalt(II) chloride, the flexible bis(pyridyl)-bis(amide) ligand L and the aromatic tricarboxylic acid H₃BTB. The structures of complexes 1–2 have been characterized by X-ray single crystal diffraction analyses, infrared spectroscopy (IR), powder X-ray diffraction (PXRD) and thermogravimetric (TG) analyses. Complex 1 is a 3D metal–organic network with the penta-nodal (2,4,4,5,6)-connected {4·6³·8·10}₂{4²·6⁵·8³}₂{4³·6³}₂{4⁶·8⁹}{6}₂ topology constructed from the 3D [Cd₅(BTB)₄]_n^2n? coordiantion framework and the protonated HL ligands. Complex 2 displays a binodal (4,4)-connected {6⁴·8·10}{6} topological 2D layered architecture based on the 1D [Co(HBTB)]_n chains and the 1D [CoL]_n chains, which are further linked by hydrogen bonding interactions to form a 3D supramolecular network. Moreover, the fluorescent properties of the cadmium(II) complex and the dyes adsorption performances of complexes 1–2 have been studied.     

Synthesis,Crystal Structures,Luminescence, Biological and Catalytic Properties of Two d10 Metal-Organic Coordination Polymers Constructed from Mixed Ligands

Two d¹⁰ metal-organic coordination polymers, [Cd₂(4-cpa)₄(bmip)₂]_n (1) and [Zn(4-cpa)₂(4,4′-bpy)]_n (2), [4-cpa = 4-chlorophenylacetate, bmip = 1,3-bis(2-methylimidazoly)propane, 4,4′-bpy = 4,4′-bipyridine], were hydrothermally synthesized and characterized by IR spectroscopy, elemental analysis, thermogravimetric analysis (TGA), powder X-ray diffraction and single-crystal X-ray diffraction. Single-crystal X-ray diffraction studies indicated that both 1 and 2 display analogous wave-like infinite chain structures. The two coordination polymers are further extended into 3D supramolecular structures through π···π stacking interactions and C–H···O hydrogen bonds for 1 and π···π stacking interactions, C–H···π stacking interactions and C–H···O hydrogen bonds for 2. Both 1 and 2 emit the intense blue luminescence at room temperature. The 4-Hcpa ligand and complexes 1 and 2 have been screened for their herbicidal activities against Brassica napus L. and Echinochloa crusgalli L. The results are compared with the activity of quizalofop-P-ethyl. Both compounds exhibit high catalytic properties on degradation of methyl orange in Fenton-like process.     

Cadmium(II)-N-Ethylimidazole Coordination Polymer via Different Coordination Environment and Chloro Bridges: Synthesis, X-ray Structure, Spectroscopic and Thermal Analysis

A novel coordination polymer [Cd₂(μ-Cl)₄(Neim)₃]_n (1) (Neim = N-ethylimidazole) was synthesized and structurally characterized by means of elemental analysis, thermal analysis, FT-IR spectrum and single-crystal X-ray diffraction. There are two different cadmium centers in 1. One of these metal centers has octahedral geometry, while the other has square pyramidal geometry. Two Neim ligands are coordinated to the Cd(II) ion in octahedral geometry while one Neim ligand is coordinated to the Cd(II) ion in square pyramidal geometry. Relatively weak C–H···Cl interactions between N-ethylimidazole molecules and chloro ions in the complex play an important role in the construction of a three-dimensional supramolecular framework. Complex 1 exhibits photoluminescence emission in solid state at room temperature.     

Preparation of a Novel Nano-scale Lead (II) Zig-Zag Metal–Organic Coordination Polymer with Ultrasonic Assistance: Synthesis,Crystal Structure,Thermal Properties,and NBO Analysis of [Pb(μ-2-pinh)N<Subscript>3</Subscript> H<Subscript>2</Subscript>O]<Subscript>n</Subscript>

A novel nano-cauliflower-shaped lead(II) metal–organic coordination polymer, [Pb(μ-2-pinh)N₃ H₂O]_n (1), was synthesized using an ultrasonic method. The nanostructure was characterized by scanning electron microscopy (SEM), X-ray powder diffraction, IR spectroscopy, elemental analysis, and thermal analysis. The compound was structurally characterized by single-crystal X-ray diffraction. The coordination compound takes the form of a zig-zag one-dimensional polymer in solid state. The coordination number of the lead(II) ions is six (PbN₄O₂) with three nitrogen atoms and one oxygen atom from two linker organic ligands, as well as one oxygen from coordinated water and one nitrogen atom from terminal coordinated azide anion. It has a stereo-chemically active lone electron pair, and the coordination sphere is hemidirected. The zig-zag 1D chains interact with neighbouring chains through weak interactions, creating a 3D supramolecular metal–organic framework. Lead oxide nanoparticles were obtained by thermolysis of the new nano coordination compound at 180 °C with oleic acid as a surfactant. The morphology and size were further studied using SEM. Natural bond orbital analyses demonstrate the electronic properties of the lead centre and other atoms.     

Sonochemical Synthesis of One-Dimensional Nano-structure of Three-Dimensional Cadmium(II) Coordination Polymer

Nano-wires and nano-rods of a new three-dimensional cadmium(II) coordination polymer, {[Cd₃(3-pyc)₄(NCS)₂(H₂O)₄]·2H₂O} _n (1); 3-Hpyc = 3-pyridinecarboxilic acid, were synthesized by a sonochemical method in two different concetrations. The morphology of the nano-structures depend strongly on reactants’ concentration. The new nano-structures were characterized by scanning electron microscopy, X-ray powder diffraction, elemental analyses and IR spectroscopy. Compound 1 was structurally characterized by single-crystal X-ray diffraction and is a three-dimensional polymer with two types of Cd(II) coordination environments.     

A new (3,3,6)-connected achiral 3D supramolecular network containing unique helical chains based on 1H-benzimidazole-5,6-dicarboxylato and Pb(II)

A new 1D Pb(II) coordination polymer, {[Pb(Hbidc)(phen)]·H₂O}_n (1), has been synthesized by a solvothermal method based on 1H-benzimidazole-5,6-dicarboxylato (H₃bidc) and 1,10-phenanthroline (phen). Complex 1 features two types of helical chains, a 1D left- and right-handed double-stranded helical chain and a supramolecular helical chain, which interweave into a new (3,3,6)-connected achiral 3D supramolecular network. Notably, the supramolecular helical chains are induced by the different spatial orientations of the 1D double-stranded helical chains. The structure and properties of 1 have been determined by single crystal X-ray diffraction, powder X-ray diffraction (PXRD), elemental analysis (EA), thermogravimetric (TG) analysis and solid state fluorescence spectra.     

Syntheses, Structures and Properties of Two 2D Transition Metal Coordination Polymers Based on Oxalate and Two Types of N-donor Auxiliary Ligands

Two new two-dimensional (2D) metal–organic coordination polymers [Co(ox)(bbbm)]·H₂O (1) and [Cu(ox)(bppdca)]·2H₂O (2) (H₂ox = oxalic acid, bbbm = 1,1-(1,4-butanediyl)bis-1H-benzimidazole and bppdca = N,N′-bis(pyridin-3-yl)-2,6-pyridinedicarboxamide) were synthesized under hydrothermal conditions and structurally characterized. Both 1 and 2 exhibit a 2D four-connected network formed by the Co^II/Cu^II ions as four-connected nodes; and, the ox anions and bbbm/bppdca ligands as linkers with a (4⁴.6²) topology as determined by single crystal X-ray diffraction. In addition, the thermal stability, electrochemical and luminescent properties for 1 and 2 were investigated.     

Coordination Behaviors and Supramolecular Interactions of 2-(2′-Pyridyl) Imidazoline: Crystal Structure of Its Two Cu(II) Complexes

Two new copper coordination complexes, [Cu(PI)(OX)(H₂O)]·H₂O (1) and [Cu(PI)(fum)(H₂O)]·H₂O (2) [PI = 2-(2′-pyridyl) imidazoline, OX^2? = dianion of oxalic acid and fum^2? = dianion of fumaric acid], were synthesized by interface diffusion method based on Cu(II) ions, PI ligands and aliphatic dicarboxylic acids. Complex 1 is a mononuclear complex which spreads into a 3D (4,9)-connected supramolecular network via hydrogen bond interactions, while complex 2 features a 1D zigzag chain with two different orientations. These two compounds are characterized by single crystal X-ray diffraction, powder X-ray diffraction, elemental analyses, infrared spectra, and thermogravimetric analyses.     

Preparation, Crystal Structures and Photoluminescence of Two New Zinc Complexes Based on 1H-Imidazo[4,5-f][1,10]-phenanthroline and Auxiliary Ligands

Two new coordination polymers [Zn(ip)(2,5-tda)(H₂O)₂] _n (1) and [Zn₂(ip)₂(5-npa)₂] _n (2) (2,5-tda = thiophene-2,5-dicarboxylic acid, ip = 1H-imidazo[4,5-f][1,10]-phenanthroline and 5-npa = 5-Nitroisophthalic acid) were synthesized and characterized by IR, elemental analysis, PXRD and X-ray diffraction. Single-crystal X-ray analyses revealed that 1 and 2 demonstrate a 1D chain structure. Complex 1 was bridged by 2,5-tda ligands in a μ₁ ? η¹:η⁰/μ₁ ? η¹:η⁰ coordination mode, and further extended into a 2D supramolecular structure by hydrogen bonding and π···π interactions. In 2, the 5-npa ligand acts as a bridging moeity, exhibiting μ₁ ? η¹:η¹/μ₁ ? η¹:η⁰ and μ₁ ? η¹:η⁰/μ₁ ? η¹:η⁰ coordination modes to link metal ions to form a 1D chain. The chains are further connected via hydrogen bonding interactions into a 2D supramolecular structure. The luminescent properties for 1 and 2 were investigated in the solid state at room temperature.