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.     

Sonochemical Synthesis and Characterization of the First Flower-Like Cadmium(II) Coordination Compound: New Precursor to Produce Pure Phase Nano-Sized Cadmium(II) Oxide

For the first time the flower-like cadmium(II) coordination compound, [Cd(2,2’-bpy)(ftfa)₂]_n (1), (2,2’-bpy = 2,2’-bipyridine; ftfa = furoyltrifluoroacetonate) is synthesized sonochemically. The new nano-structure was characterized by scanning electron microscopy, X-ray powder diffraction, elemental analyses and IR spectroscopy. Single crystalline material is obtained using a heat gradient applied to a solution of the reagents. The thermal stability of compound is studied by thermogravimetric and differential thermal analyses. After calcinations of nano-sized 1 at 400 °C, pure phase nano-sized Cd(II) oxide was produced. The average size of the nanoparticles is estimated by the Scherrer equation (diameter ≈ 25 nm). The morphology and size of the prepared Cd(II)O samples are examined by SEM.     

Sonochemical Synthesis of a New Lead(II) Coordination Polymer with 2-Quinoline Carboxylate Ligand: A Precursor for the Preparation of Nano-structured Lead(II) Oxide

Crystalline and nano-structure of a new Pb(II) coordination polymer, [Pb(NO₂)(2-quc)]_n (1), {Hquc?=?2-quinoline carboxylic acid} is synthesized via heat gradient and sonochemical methods, respectively. The newly synthesized structures are characterized by scanning electron microscopy (SEM), X- ray powder diffraction (XRD), IR and ¹HNMR spectroscopies, elemental analyses and single crystal X-ray diffraction is used to understand the exact structure of the crystalline 1. Thermal stability of nano and bulk samples of compound 1 are studied and compared through thermal gravimetric and differential thermal analyses. PbO nanoparticles are then produced by calcination of the nano-structure of compound 1 at 600?°C. The obtained PbO is characterized by XRD and SEM analyses.     

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.     

Sonochemical Synthesis of Nano-structured Lead(II) Coordination Polymer with 2-Aminonicotinic Acid: Thermal, Structural and X-ray Powder Diffraction Studies

A new one-dimensional crystalline and nano-structured Pb(II) coordination polymer, [Pb(2-anc)₂(NO₃)₂] _n (1) {2-Hanc?=?2-aminonicotinic acid}, were synthesized via heat gradient and sonochemical methods. The new produced nano-structure was characterized by scanning electron microscopy, X-ray powder diffraction, IR spectroscopy, and elemental analyses. Structural characterization by single crystal X-ray diffraction exhibits two-dimensional polymeric units for compound 1. Thermal stability of nano and bulk samples of compound 1 were studied and compared. PbO nano-particles was then obtained via calcination of nano-compound 1 at high and low temperatures. The calcinations result demonstrates that compound 1 may be suitable precursor for the preparation of nanoscale lead(II) oxide without need for special conditions like high temperature, long times and pressure control.     

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.     

Cobalt(II), Zinc(II) and Cadmium(II)-Squarate Complexes with N-Methylimidazole

Three M(II)-squarate complexes, [Co(sq)(H₂O)(Nmim)₄] (1), [Zn(μ_1,3-sq)(H₂O)₂ (Nmim)₂] _n (2) and [Cd(μ_1,3-sq)(H₂O)₂(Nmim)₂] _n (3) (sq = squarate, Nmim = N-methylimidazole) have been synthesized and characterized by elemental, spectral (IR and UV–Vis.) and thermal analyses. The molecular structures of the complexes have been investigated by single crystal X-ray diffraction technique. The squarate ligand acts as two different coordination modes as a monodentate (in 1) and bis(monodentate) (O ^1– O ³ ) bridging ligand (in 2, 3). The Co(II) atom has a distorted octahedral geometry with the basal plane comprised of three nitrogen atoms of Nmim ligands and a oxygen atom of squarate ligand. The axial position is occupied by a nitrogen atom of Nmim and one aqua ligand. The crystallographic analysis reveals that the crystal structures of 2 and 3 are one-dimensional linear chain polymers along the c and b axis, respectively. The configuration around each metal(II) ions are distorted octahedral geometry with two nitrogen atoms of trans-Nmim, two aqua ligands and two oxygen atoms of squarate-O¹,O³ ligand. These chains are held together by the C–H···π, π···π and hydrogen-bonding interactions, forming three-dimensional network.     

Synthesis and Characterization of ZnO Nanoparticles via Thermal Decomposition of Two Zinc(II) Supramolecular Compounds

A new nano-sized Zn(II) complex, [Zn(5,5′-dtbu-2,2′-bipy)Cl₂] _n (1) was synthesized and its structure determined by X-ray crystallography. The new nano-sized complex was prepared at oleic acid as a surfactant at 280 °C and characterized by scanning electron microscopy, elemental analyses and IR spectroscopy. The ZnO nano-particles were synthesized from thermolysis of nano-compound 1 at 600 °C and similar compound, [Zn(5,5′-dimethyl-2,2′-bipy)Cl₂] _n (2), at two different methods. SEM images show the average size of ZnO nano-particles are 78 and 50 nm for the compounds 1 and 2, respectively.     

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 and Reactivity of Iron(II) Complexes with a New Tripodal Imine Ligand

A new tripodal imine ligand tris(2-(propan-2-ylideneamino)ethyl)amine (imine₃tren) was prepared in order to stabilize high valent iron-oxido complexes. Iron complexes were synthesized in template reactions from iron(II) salts, tris(2-aminoethyl)amine (tren) and acetone. Due to the reversibility of the imine formation, complexes with different ligands were obtained depending on the reaction conditions. Three complexes, [Fe(imine₃tren)(OAc)₂] ( 1 ), [Fe(imine₃tren)(OAc)]OTf ( 2 ) and [(imine₃tren)₂Fe₂(F)₂](SbF₆)₂ ( 3 ), could be synthesized and structurally characterized. However, reactions with hydrogen peroxide, iodosobenzene or ozone did not lead to any kind of “oxygen adduct” complex that could be spectroscopically observed.     

Isomer Directed Synthesis of Two 3D Cadmium(II) Compounds: Structure Variation and Energetic Performance

Two inorganic mixtures of copper and sodium compounds have been synthesized and characterized with different measurement techniques. The thermal property of these mixtures has been studied to low temperature up to 223 from 573 K with DSC. The specific heat capacity of this mixture has been measured in atmospheric O₂ at a rate of 10 K min^?1 from 573 to 223 K and vice versa in two thermal cycles. The net specific heat capacity of these mixtures is found endothermic in first and second thermal cycles. The net specific heat capacity of 0.5Cu₂(PO₄)(OH); 3.5CuH(PO₄)₂·H₂O; 2NaHSO₄·H₂O (CuPHS) during first thermal cycle is ?71203.05 J kg^?1 K^?1 and in second thermal cycle is ?73881.67 J kg^?1 K^?1 between temperature range of 303–223 K. The net specific heat capacity of mixture 0.5Cu₂(PO₄)(OH); 3.5CuH(PO₄)₂; 2Na₂SO₄(CuPS) in first thermal cycle is ?21158.37 J kg^?1 K^?1 and in second thermal cycle is?45739.92 J kg^?1 K^?1 between temperature range of 298–573 K. As both mixtures are endothermic in nature in all cycles, it can be used as heat storage material.The average crystallite size of mixture 0.5Cu₂(PO₄)(OH); 3.5CuH(PO₄)₂·H₂O; 2NaHSO₄·H₂O and 0.5Cu₂(PO₄)(OH); 3.5CuH(PO₄)₂; 2Na₂SO₄ is ~47 and ~17.3 nm, respectively.     

Synthesis, Characterization and Antifertility Activity of New Unsymmetrical Macrocyclic Complexes of Tin(II)

A new series of unsymmetrical macrocyclic complexes of tin(ll) has been prepared by the template process using bis(3-oxo-2-butylidene)propane-1,3-diamine as precursor. This affords a method to synthesize these complexes with various ring sizes. The tetradentate macrocyclic precursor [N(4)mL] reacts with SnCl(2) and different diamines in a 1:1:1 molar ratio in refluxing methanol to give complexes of the type [Sn(N(4)mL)Cl(2)]. The ring expansion has been achieved by varying the diamine between the two diacetyl amino nitrogen atoms. The macrocyclic precursor and its metal complexes have been characterized on the basis of elemental analysis, molar conductance, molecular weight determinations, IR, (1)H NMR,(13)C NMR, (119)Sn NMR and electronic spectral studies. An octahedral geometry around the metal ion is suggested for these complexes. On the basis of molecular weights and conductivity measurements, their monomeric and non-electrolytic nature has been confirmed. The precursor and complexes have been screened in vitro against a number of pathogenic fungi and bacteria to assess their growth inhibiting potential. The testicular sperm density and testicular sperm morphology, sperm motility, density of cauda epididymal spermatozoa and fertility in mating trails and biochemicals parameters of reproductive organs have been examined and discussed.     

Synthesis and Anticancer Evaluation of New Indole-Based Tyrphostin Derivatives and Their (p-Cymene)dichloridoruthenium(II) Complexes

New N-alkylindole-substituted 2-(pyrid-3-yl)-acrylonitriles with putative kinase inhibitory activity and their (p-cymene)Ru(II) piano-stool complexes were prepared and tested for their antiproliferative efficacy in various cancer models. Some of the indole-based derivatives inhibited tumor cell proliferation at (sub-)micromolar concentrations with IC₅₀ values below those of the clinically relevant multikinase inhibitors gefitinib and sorafenib, which served as positive controls. A focus was set on the investigation of drug mechanisms in HCT-116 p53-knockout colon cancer cells in order to evaluate the dependence of the test compounds on p53. Colony formation assays as well as experiments with tumor spheroids confirmed the excellent antineoplastic efficacy of the new derivatives. Their mode of action included an induction of apoptotic caspase-3/7 activity and ROS formation, as well as anti-angiogenic properties. Docking calculations with EGFR and VEGFR-2 identified the two 3-aryl-2-(pyrid-3-yl)acrylonitrile derivatives 2a and 2b as potential kinase inhibitors with a preferential activity against the VEGFR-2 tyrosine kinase. Forthcoming studies will further unveil the underlying mode of action of the promising new derivatives as well as their suitability as an urgently needed novel approach in cancer treatment.     

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.     

Effects of the Molecular Design on the Supramolecular Organization of Luminescent Pt(II) Complexes

Self‐assembly is an extremely important processes that allows the constructions of large supramolecular architectures through encoded information present in the components. A subtle change in the chemical structure of the single unit can dramatically change the kinetics and thermodynamic pathway. We demonstrate that a minor change, introduced by designing the structure of a family of Pt(II) complexes can influence the color of the emission of the assemblies and their kinetic behaviour. The assembly processes, visualized by confocal microscopy, and detailed through photophysical measurements, reveal that the establishment of intermolecular interactions, as well as electronic factors lead to completely different assemblies in solution of the platinum compounds. A correlation between the observed behaviour and the chemical structure of the compounds is discussed and the results indicate a strong kinetic control of the supramolecular processes.     

新型多吡啶铂(Ⅱ)络合物的设计、合成及性能研究

由于特殊的分子构型及电子排布,具有平面四边形构型的多吡啶Pt(Ⅱ)络合物能够产生许多特殊的、具有潜在应用价值的激发态性质．本论文设计、合成了一系列以三联吡啶、6-苯基-2,2’-二联吡啶、菲啰啉为主配体,取代苯乙炔为辅助配体的多吡啶Pt(Ⅱ)络合物,系统地研究了它们的光物理性质,取得如下有意义的研究结果: