Controlled radical polymerization of n-hexadecyl methacrylate mediated by tris(2,2′-bipyridine)iron(III) complexes

Poly(n-hexadecyl methacrylate) (PHMA) with narrow molecular weight distribution has been synthesized by atom transfer radical polymerization (ATRP) and reverse ATRP of n-hexadecyl methacrylate (HMA) at 80 °C in N, N-dimethylformamide (DMF) using the CBr₄/tris(2,2′-bipyridine)iron(III) complex initiation system in the presence of 2,2′-azobisisobutyronitrile (AIBN). From the kinetic studies and molecular weight data, it reveals the controlled nature of polymerization. The effect of various reaction parameters on number-average molecular weight (M _n ) and molecular weight distribution (M _w /M _n ) have been investigated. For the reverse ATRP, the catalyst tris(2,2′-bipyridine)iron(III)complex, [Fe(bpy)₃]³⁺, played an important role in polymerization rate and M _w /M _n . The resulting PHMA that obtained by reverse ATRP shows the best control of molecular weights and its distribution as compared to normal ATRP system. PHMA has been characterized by different techniques such as GPC, XRD and NMR spectroscopy.     

Metal-Ion Type Effect on the Crystal Structure and Optical Properties of 2,2′-bipyridine Complexes of Pb(II) and Cd(II)

To investigate the effect of metal ion type on the crystal structure and optical and thermal behaviors of coordination compounds, two homometal and one heterometal 2,2′-bipyridine complexes of Pb(II) and Cd(II) have been synthesized and characterized by elemental analysis, PXRD, FT-IR and single crystal X-ray diffraction. Crystal structure analysis of heterometal coordination polymer, [Pb₂Cd(2,2′-bipy)₄(NO₃)₆]_n, displays the attendance of a centrosymmetric 1D coordination polymer that crystallizes in the triclinic system with the space group of \({\text{p}}_{1}^{ - }\). Thermal behavior of prepared coordination compounds was examined under air atmosphere by thermogravimetric analysis. The study of optical properties of compounds showed that metal ion type of coordination compounds is influential on their photophysical properties. Moreover, heterometal coordination polymer was doped into a PVK:PBD blend in two different concentrations as a light emitting material in the fabrication of two organic light-emitting diodes.     

Ion exchange and charge transport properties of polymeric tris(4-vinyl-4′-methyl-2,2′-bipyridine) ruthenium(II) films

Multiply charged electroactive anions [IrCl ₆ ^2? , Fe(CN) ₆ ^3? , and W(CN) ₈ ^4? ] are electrostatically incorporated in polymeric films of tris(4-vinyl-4′-methyl-2,2′-bipyridine) ruthenium(II) [poly-Ru(vbpy) ₃ ²⁺ ] from aqueous trifluoroacetate solution. Values of apparent diffusion coefficients (D _ct) and heterogenous electron transfer rates (k _et) are measured for these anions as a function of their relative concentration (Γ _M/Γ _Ru) in the film.D _ct andk _et decrease systematically asΓ _M/Γ _Ru increases in a manner that is independent of charge and chemical identity of the ion. This result suggests that a nonchemical process, presumably electrostatic cross-linking, limits diffusional motion and is responsible for the decrease inD _ct andk _et with increasing anion content. Protonated polyvinyl-pyridine films exhibit similar ranges and variations inD _ct andk _et, which suggest similar structures and mechanisms of charge transport for these films and poly-Ru(vbpy) ₃ ²⁺ .     

A novel one-dimensional single helix derived from 2,2′-bipyridine based Zn(II) species directed self-assembly with 1,2-benzenedicarboxylate

The self-assembly assisted by 2,2^′-bipyridine (2,2^′-bpy) protected zinc(II) species with 1,2-benzenedicarboxylate (1,2-BDC) has yielded a novel one-dimensional single helical coordination polymer of [Zn(2,2′-bpy)(1,2-BDC)(H₂O)]_n in a racemate of right- and left-handed helices, which was crystallographically studied and thermally analyzed.     

Oxidation of Benzene Catalyzed by 2,2′-Bipyridine and 1,10-Phenantroline Cu(II) Complexes

The use of mononuclear Cu(II) 2,2′-bipyridine and 1,10-phenantroline complexes as catalysts in the oxidation of benzene, using hydrogen peroxide and tert-butyl hydroperoxide as oxidant in CH₃CN/H₂O solution is presented. The reactions were carried out at 25 and at 50 °C. The complexes [Cu(bipy)₃]Cl₂ · 6H₂O (1), [Cu(bipy)₂Cl]Cl · 5H₂O (2), [Cu(bipy)Cl₂] (3), [Cu(phen)₃]Cl₂ · 7H₂O (4), [Cu(phen)₂Cl]Cl · 5H₂O (5), [Cu(phen)Cl₂] (6) were able to oxidize benzene into phenol, hydroquinone and p-benzoquinone. Highest conversion (22%) was obtained using [Cu(Phen)Cl₂] (6) as catalyst.     

Aldehyde-decorated 2,2′-bipyridine and 2,2′:6′,2″-terpyridine ruthenium(II) complexes: Convenient scaffolds for supramolecular chemistry

Two new aldehyde-decorated tpy and bpy-containing ruthenium(II) complexes, [Ru(1)(bpy)₂][PF₆]₂ and [Ru(1)(tpy)Cl][PF₆] in which 1 is 5,5′-bis(4-formylphenyl)-2,2′-bipyridine, have been prepared and fully characterized. The packing in both solid state structures involves extensive O_aldehyde···HC_pyridine contacts, but π-stacking interactions are important only between [Ru(1)(tpy)Cl]⁺ cations.     

A 3D Mesomeric Supramolecular Structure of a Cu(II) Coordination Polymer with 1,1′-Biphenyl-2,2′,3,3′-tetracarboxylic Acid and 5,5′-Dimethyl-2,2′-bipyridine Ligands

A novel metal–organic framework {[Cu(H₂bptc)(cbpy)(H₂O)]·(H₂O)} _n (1) has been hydrothermally synthesized through reaction of 1,1′-biphenyl-2,2′,3,3′-tetracarboxylic acid (H₄bptc) with Cu(II) salt in the presence of ancillary nitrogen ligand 5,5′-dimethyl-2,2′-bipyridine (cbpy), and its structure was determined by X-ray diffraction and characterized by elemental analysis, and IR spectrum. The title compound crystallizes in monoclinic space group P2₁/c. Both right- and left-handed helices are detected in the structure. In the ab-plane, adjacent chains are homochiral and parallel to each other, which are connected together by hydrogen bonds to form a 2D supramolecular structure. The supramolecular layers with opposite chirality are arranged alternatively along the c-axis to form a 3D mesomeric supramolecular structure through π···π interactions. The thermal stability of the complex 1 was studied by thermal gravimetric and differential thermal analysis.     

The dimeric and two-dimensional copper(II) complexes constructed from salicylic acid and 4,4′-bipyridine

Two novel complexes, [Cu₂(Hsal)₄(4,4^′-bipyridine)(H₂O)₂(DMF)₂] (1) (H₂sal=salicylic acid) and {[Cu(Hsal)₂(4,4^′-bipyridine)](H₂O)(H₂sal)}_n (2), were synthesized by layered-solution method and structurally characterized. Geometries of copper atoms in both complexes exhibit square pyramidal. Complex 1 is a dimer and hydrogen bonds between water and DMF molecules extend the structure into 1D hydrogen bonding network. Complex 2 consists of two-dimensional square framework structure.     

Carbonyl and chloro complexes of ruthenium(II) containing 3,3′-diester-2,2′-bipyridyl ligands

A series of 3,3′-dialkoxycarbonyl-2,2′-bipyridines (alkyl=Me, Et, i-Pr, i-Bu) has been prepared in good yield from 1,10-phenanthroline. The synthesis and characterization of the corresponding trans-(Cl)-Ru(L)(CO)₂Cl₂ and cis-Ru(L)₂Cl₂ complexes are described.     

Syntheses and Characterization of Two New M(II)-5,5′-dimethyl-2,2′-bipyridine (M = Cd and Pb) Coordination Polymers and Study of Their Thermal and Electrochemical Properties

Two new cadmium(II) and lead(II)-thiocyanato coordination polymers with 5,5′-dimethyl-2,2′-bipyridine (5,5′-dm-2,2′-bpy) as chelating ligands were synthesized and characterized by elemental analysis, IR and ¹H NMR spectroscopy and by X-ray crystallography. Thermal and electrochemical properties were also studied as well. These complexes have formed formula [Cd(5,5′-dm-2,2′-bpy)(NCS)₂]_n (1) and [Pb(5,5′-dm-2,2′-bpy)(CH₃COO)(NCS)]_n (2). The coordination numbers of Cd^II in 1 and Pb^II in 2 are six (CdN₄S₂) and seven (PbN₃O₃S₂), respectively. In 2, “stereo-chemically active” electron lone pairs and the coordination spheres were hemidirected. Bridging properties of thiocyanato anions in 1 and 2 created one- and two-dimensional coordination polymers, respectively. The supramolecular features in these complexes were guided and controlled by weak directional intermolecular interactions.     

Inhibition of 2,2′-azobis(2,4-dimethylvaleronitrile)-induced lipid peroxidation by sesaminols

We found that sesaminols, a mixture of sesaminol and its stereoisomers, are potent inhibitors of the oxidation of low-density lipoprotein induced by 2,2′-azobis(2,4-dimethylvaleronitrile). Although sesaminols strongly inhibit lipid peroxidation related to their ability to scavenge free radicals, their antioxidant effects have not been investigated. To confirm the involvement of the phenolic moiety in the sesaminol structure in antioxidant activity, sesaminols were reacted with 2,2′-azobis(2,4-dimethylvaleronitrile). The reaction products were isolated by high-performance liquid chromatography and found to have a 1-cyano-1,3-dimethyl-butyl-peroxyl group in their structures. These chemical structures suggest that the sesaminols reacted with the alkylperoxyl radicals to form four major reaction products that are stereoisomers of each other, although the stereochemistry of each isomer has not yet been confirmed. Further instrumental analyses of the reaction products may increase our understanding of the antioxidant activity of sesaminols.     

Use of HPLC in the identification of cis and trans-diaquabis(2,2′-bipyridine)ruthenium(II) complexes: crystal structure of cis-[Ru(H2O)2(bpy)2](PF6)2

[Ru(H₂O)₂(bpy)₂](PF₆)₂ complex was obtained by reacting HPF₆ in a [Ru(CO₃)(bpy)₂] aqueous solution. The complex can exist as cis and trans isomers and usually has been used in the preparation of several ruthenium–bipyridine species. Despite the possibility to have contamination of a specie in another, there is no analytical control involving the characterization of both complexes. Based on this we have proposed the use of high-performance liquid chromatography (HPLC) as an analytical technique to control the purity of cis and trans isomers. The separation was performed using a CLC-ODS column. The cis isomer eluted at 9.4 min while trans isomer eluted at 4.3 min. In aqueous solution the trans and cis isomer configurations were confirmed by NMR spectra (¹H). The attribution of cis isomer was also made based on the X-ray crystal structure (monoclinic, P2_1/c, a=12.320(2), b=13.852(2), c=34.220(3) Å, β=91.89(1)°, Z=8) which is reported. The six-coordinated ruthenium atom is chelated by two bipyridines and two molecules of H₂O.     

Thermal and Fluorescence Properties of New Nanostructured Hg(ll) -2,2′-Bipyridine Derivative Complexes

Two new nano-structured Hg(II) supramolecular complexes, [Hg(5,5′-di-t-but-bpy)(μ-Br)Br]₂[Hg(5,5′-di-t-but-bpy)Br₂](1) and [Hg(5,5′-di-t-but-bpy)I₂] (2) were synthesized by the sonochemical method. The structures of 1 and 2 were characterized by elemental analysis, IR, ¹H-NMR, and ¹³C-NMR spectroscopy and single crystal X-ray diffraction. Their thermal stabilities were studied by thermogravimetric and differential thermal analyses. Solid-state luminescent spectra of 1 and 2 indicate a fluorescent broad emission band between 304 and 404 nm with excitation at 284 nm. These nanostructured coordination polymers were characterized by scanning electron microscopy, elemental analysis, and IR spectroscopy.     

Studies on uptake behavior of Hg(II) and Pb(II) by amine modified glycidyl methacrylate–styrene–N,N′-methylenebisacrylamide terpolymer

The removal of mercury and lead ions from aqueous solutions investigated by ethylenediamine, diethylenetriamine and tetraethylenepentamine functionalized polymeric adsorbent. The adsorbent was prepared by amination of terpolymer synthesized from glycidylmethacrylate, styrene and N,N′-methylenebisacrylamide. In the single metal species system (only mercury or lead ions are present) poly(glycidylmethacrylate–ethylenediamine) (PGMA–EDA), poly(glycidylmethacrylate–diethylenetriamine) (PGMA–DETA), and poly(glycidylmethacrylate–tetraethylenepentamine) (PGMA–TEPA) were found to adsorb lead or mercury ions with a slightly higher adsorption uptake capacity for lead than mercury ions. Among the three functionalized polymers poly(glycidylmethacrylate–diethylenetriamine) (PGMA–DETA) shows faster and higher adsorption capacity than poly(glycidylmethacrylate–ethylenediamine) (PGMA–EDA), poly(glycidylmethacrylate–tetraethylenepentamine) (PGMA–TEPA). The natural pH of both the metal ions was found to be most suitable for uptake. The uptake of Hg(II) and Pb(II) ions was investigated by using batch technique. The maximum adsorption capacities of Pb ions were predicted to be 4.74, 4.76 and 4.73 mmol/g and the maximum Hg(II) ion uptakes were found to be 4.76, 4.80 and 4.21 mmol/g respectively for PGMA–EDA, PGMA–DETA and PGMA–TEPA resins at their natural pH. The uptakes of Hg(II) and Pb(II) ions on the resins were found to follow Langmuir adsorption isotherm and pseudosecond order kinetics.     

Two-dimensional assembling of 4,4′-bipyridine and 4,4′-azopyridine bridged iron (II) linear coordination polymers via hydrogen bond

Novel two-dimensional polymers, [Fe(L¹)(H₂O)₂(NCX)₂] · L¹ (L¹ = 4,4′-bipyridine (bipy)) (1, 2) and [Fe(L²)(CH₃OH)₂-(NCX)₂] · L² (L² = 4,4′-azopyridine (azpy)) (3) and X = S (1,3),Se (2), have been synthesized and characterized by X-ray crystallography. The structures reveal the formation of trans-L-bridged [Fe(NCX)₂(Y)₂] where Y = H₂O, CH₃OH linear chains assembled into two-dimensional networks by hydrogen bonds between the uncoordinated ligand L and the coordinated solvent molecules.     

Kinetic and Thermodynamic Separation of Cu(II) and Fe(III) by Liquid-Liquid Extraction with a β-Hydroxy-oxime in Toluene

Abstract

A quantitative study of the thermodynamic and kinetic separation of Cu(II) and Fe(III) by liquid-liquid extraction with toluene solutions of the oxime 2-hydroxy-5-t-octyl (acetophenone oxime) has been conducted. On the basis of the stoichiometry, equilibrium constants, rate laws and rate constants of the extraction reactions of Cu(II) and Fe(III) an equation has been derived which describes how the separation of Cu from Fe varies with the chemical composition of the system, the hydrodynamics of the extracting apparatus and the contact time between the aqueous and the organic phases. Our results show that separations which are not feasible thermodynamically are possible when the contact time between the two phases is kept much shorter than that required to reach equilibrium.     

Grafting of High α-Cellulose Pulp Extracted from Sunflower Stalks for Removal of Hg (II) from Aqueous Solution

Dissolving pulp containing 95.5% α-cellulose was extracted from sunflower stalks. The pulped sunflower stalks (PSFS) were used as starting material for grafting with acrylamide (Aam). All factors affecting the grafting reaction were examined. These factors include liquor ratio (LR), ceric ammonium nitrate (CAN) concentration as a catalyst, Aam concentration, as well as reaction time and temperature. The grafted PSFS (GPSFS) samples were characterized by estimation of nitrogen %. The GPSFS was utilized as adsorbent material to remove Hg (II) ions from aqueous solutions. All factors affecting adsorption process were examined. These factors include pH, adsorbent concentration, temperature, and agitation time. The adsorption data show that the maximum adsorption capacity, q_e, of Hg (II) onto GPSFS is 625 mg/g. The adsorption data also showed that the adsorption of Hg (II) onto GPSFS obeys Langmuir and Freundlich isotherms.