Coordination polymers, 1. Magnetic,spectral, and thermal properties of coordination polymers derived from terephthalaldehyde bis(S-benzyldithiocarbazate)

New Mn(II), Fe(II), Co(II), Ni(II), Cu(II), and Zn(II) coordination polymers of Schiff base ligand derived from terephthalaldehyde and S-benzyldithiocarbazate have been synthesized in DMF media. The coordination polymers have been characterized by their elemental analysis, magnetic susceptibility, and by electronic and infrared spectral measurements. The thermal stability of each polymer was found out by thermogravimetric analysis. The thermal stability of coordination polymers obtained from thermograms has the following order: $ {\rm Zn} \simeq {\rm Fe} > {\rm Co} > {\rm Ni} > {\rm Min} \simeq {\rm Cu}$ Mn(II), Fe(II), Co(II), and Ni(II) coordination polymers are of a six-coordinated octahedral structure while Cu(II) and Zn(II) coordination polymers are found to be four-coordinated square planar and tetrahedral structure, respectively. The ligand-field and nephelauxetic parameters have been determined from the spectra, using ligand-field theory of spin-allowed transitions which are found consistent with six-coordinate structure for Mn(II), Fe(II), Co(II), and Ni(II) coordination polymers. Elemental analyses indicates a ligand: metal ratio of 1 : 1 in all the coordination polymers and the association of water molecules with central metal atom in case of Mn(II), Fe(II), Co(II), and Ni(II) coordination polymers.     

Effect of orientation on electrical properties of polymers

This article deals with the effect of orientation on the electrical properties (tangent of the angle of dielectric losses tan δ, electric strength E, and lifetime τ) of polymer films. It is shown that the orientational stretching of PVC and PC films leads to the change of the temperature position of dipole segmental losses and reduces the value of tan δ in the maximum of this region. Under the orientation the electric strength of PE and PVC films increases considerably, and the lifetime τ increases under the high strengths of the field, and reduces under the low ones. The mechanical loads causing no orientation only reduce the lifetime of the polymer films.     

Coordination polymers, 4. Electrical properties of some bisphenolic chelate polymers

The electrical properties of Ni(II) and Cu(II) chelate polymers of bis(2,4-dihydroxybenzaldehyde), bis(2,4-dihydroxyacetophenone), bis(2,4-dihydroxybenzophenone), bis(2,4-dihydroxybenzaldehyde)ethylenediimine, bis(2,4-dihydroxyacetophenone)-ethylenediimine, bis(2,4-dihydroxybenzophenone)ethylenediimine and bis(2,4-dihydroxyacetophenoneimine) and aromatic acid chlorides have been studied. The chelate polymers with the most rigid structure were found to have the highest conductivities.     

Synthesis and properties of novel aromatic polyimides derived from bis(p-aminophenoxy)methylphenylsilane

A novel siloxane-containing diamine, bis(p-aminophenoxy)methylphenylsilane (BAMPS), was synthesized from the condensation of dichloromethylphenylsilane with p-aminophenol in the presence of triethylamine. A series of BAMPS-based aromatic polyimides were prepared from BAMPS and various aromatic tetracarboxylic dianhydrides by the usual two-step procedure including ring-opening polyaddition to poly(amic acid)s and subsequent cyclodehydration to polyimides. The inherent viscosities of poly(amic acid)s III_a - III_f ranged from 0.09 to 0.36 dL g⁻¹ in N,N-dimethylacetamide at a concentration of 0.5 g dL⁻¹ at 30°C. The inherent viscosities of polyimides were between 0.06 and 0.32 dL g⁻¹ in various solvents at 30°C. Polyimides, especially IV_c and IV_f , were soluble in a wide range of organic solvents such as N-methyl-2-pyrrolidinone, concentrated H₂SO₄, N,N-dimethylacetamide, N,N-dimethylformamide, and dimethyl sulfoxide. The polyimides were characterized by elementary analysis, IR spectra, TGA, and DSC. They also had glass transition temperatures ranging from 128 to 181°C. The 10% mass loss temperature was recorded in the range of 404–443°C in nitrogen and of 315–339°C in oxygen. © 1997 John Wiley & Sons, Inc.     

Syntheses,structures and photocatalytic properties of three copper(II) coordination polymers

Three coordination polymers [Cu₂(obtz)₂(tdc)₂]_n (1), {[Cu(obtz)₂(H₂O)₂][Cu₂(obtz)₂(sip)₂]5.5H₂O}_n (2) and [Cu(obtz)(nip)]_n(3) were synthesized by the hydrothermal reaction (obtz = 1.2-bis(1,2,4-triazol-1-ylmethyl)benzene, tdc = 2.5-thiophenedicarboxylate, sip = 5-sulfoisophthalate, nip = 5-nitroisophthalate). 1 shows a ladder-like one-dimensional chain with two side arms. 2 is comprised of two distinct and crystallographically independent polymeric motifs. The first motif in 2 is the ladder-like one-dimensional anionic chain with two side arms. The second motif in 2 is the cationic chain. 3 exhibits the intriguing 2-fold interpenetrated network based on the undulated 2D (4.4) network. 1, 2 and 3 are good photocatalysts for the degradation of methyl orange (MO) under UV irradiation.     

Fixed helical Cd(II) coordination polymers assembled from diastereopure Schiff-base ligands derived from condensation of acetylacetone with 1S,2S- and 1R,2R-cyclohexanediamine

The 1:1 interaction of the diastereopure Schiff bases (1S,2S)-bis(acetylacetone)-cyclohexanediimine (L¹) and (1R,2R)-bis(acetylacetone)cyclohexanediimine (L²) with CdI₂ yields the new helical metal coordination polymers [CdL¹I₂]_n (1) and [CdL²I₂]_n (2). The respective X-ray structures, as expected, confirmed 1 and 2 to be enantiomeric, existing as right-handed (P) and left-handed (M) helical chains in which both L¹ and L² are formally present in their (unusual) uncharged ketoamine form, with the (protonated) amine nitrogens not coordinated. The Cd(II) centres in 1 and 2 display distorted tetrahedral coordination geometries being bound to two iodo ligands and two oxygen donor atoms from individual ketoamine domains belonging to different Schiff base ligands.     

Syntheses,structures and luminescence of two cadmium entangled coordination polymers based on bis(imidazole) and biscarboxylate ligands

Two entangled coordination polymers [Cd₂(bib)(bdc)₂]_n (1) and [Cd₂(bib)(bda)₂]_n (2) were synthesized by the hydrothermal reaction (bib = 1,4-bis(2-methyl-imidazol-1-yl)butane, bdc = 1,2-benzenedicarboxylate, bda = 1,4-benzenediacetate). 1 exhibits an unusual 6-connected self-catenated 3D network based on Cd₂(COO)₂ dimer with the point symbol of (4⁴·6¹⁰·8). 2 exhibits a 3-fold interpenetrating 3D pcu network based on Cd₂(COO)₂ dimer. The different conformations of bib ligands (the anti–anti–anti conformation in 1 and gauche–anti–gauche conformation in 2) play the key role in the construction of different structures in 1 and 2. The luminescence and thermal stability were investigated.     

Coordination polymers. 7. Synthesis and characterization of some polychelates derived from bisphenolic complexes

Chelate polyesters and polysiloxanes derived from bisphenolic complexes with some bivalent ions as copper, nickel, cobalt, iron, zinc have been synthesized. The polychelates are studied in terms of spectral, thermal, magnetic, and electrical properties; the probable structures of these polymers have been proposed.     

Three new d10 coordination polymers based on 2-(2-pyridyl)benzimidazole ligand: Synthesis,structures and properties

Three coordination polymers containing 2-(2-pyridyl)benzimidazole (PyHBIm) ligand, namely {[Zn₃(PyBIm)₃(PyHBIm)₂(tma)(H₂O)]?H₂O}_n (1), [Zn(PyHBIm)(oba)]_n (2), [Cd(PyHBIm)(oba)]_n (3), (tma = trimesate, oba = 4,4′-oxybis-(benzoate)), have been prepared through hydrothermal reaction. Compound 1 exhibits one-dimensional (1D) helical structure. However, compounds 2 and 3 display 1D meso-helical structure. These 1D structures are further assembled into three-dimensional (3D) networks through aromatic π–π stacking interactions and hydrogen bonding interactions. Moreover they all exhibit strong photoluminescence at room temperature and may be good candidates for potential luminescence materials.     

The synthesis of selenium condensation polymers using bis(2-hydroxyethyl) selenide and bis(2-aminoethyl) selenide

Procedures were developed for the large-scale synthesis of bis(2-hydroxyethyl) selenide and bis(2-aminoethyl) selenide. These bifunctional selenides were converted into a series of polyesters, polyureas, and polyurethanes. Methods of syntheses and properties of these condensation polymers are described.     

Effect of iodine incorporation on the electrical properties of amorphous conducting carbon films

In this work, the influence of iodine incorporation on the electrical properties of amorphous conducting carbon films, prepared by the vapor phase pyrolysis of maleic anhydride, is reported and discussed. X-ray diffraction (XRD) and scanning electron microscopy (SEM) studies reveal structural changes in the system. The anomalous behavior in the electrical properties of the intercalated system at low temperatures is investigated. The system shows a positive temperature coefficient of resistance (TCR) at low temperatures, which suggests reasons for the induced ordering of the system at low temperatures with the iodine incorporation. Also, a systematic increase in the conductivity of the sample is observed. The crossover temperature depends on the disorder in the system. The results indicate the possibility of metal-insulator (M-I) transition as a function of preparation temperature, iodine concentration and magnetic field.     

Four coordination polymers derived from 4-amino-3,5-bis(3-pyridyl)-1,2,4-triazole and copper sulfate

The reaction of 4-amino-3,5-bis(3-pyridyl)-1,2,4-triazole (3-bpt) with copper sulfate in EtOH/H₂O solvent yields four coordination polymers [Cu(3-bpt)(H₂O)₄](SO₄)·H₂O (1), [Cu(3-bpt)(H₂O)₄][Cu(3-bpt)(H₂O)₃(SO₄)](SO₄)·7H₂O (2), [Cu(3-bpt)(H₂O)₃(SO₄)]·2H₂O (3) and [Cu(3-bpt)(H₂O)(SO₄)] (4), showing one-dimensional undulated chain, zigzag chain and two-dimensional network. The formations of compounds 1, 2 and 3 are controlled by the EtOH/H₂O ratio. The synthesis of compound 4 may be controlled by the EtOH/H₂O ratio and the temperature because it is prepared under solvothermal condition. The thermal properties have been investigated.     

Lanthanide coordination polymers constructed from 5-(4-pyridyl)-isophthalic acid: Synthesis,structure and photoluminescent properties

Nine lanthanide coordination polymers [Ln₂(pyip)₃(H₂O)₄·DMF·3H₂O]_n (Ln = Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho) based on the pyip^2 − ligand {H₂pyip = 5-(4-pyridyl)-isophthalic acid} have been synthesized under solvothermal conditions. X-ray crystallographic studies reveal that 1–9 are isostructural and crystallize in the triclinic system, space group P2₁/c, and exhibit a 3D framework. Topological analysis reveals that the 3D framework can be simplified to a uninodal 6-connected pcu alpha-Po primitive cubic type structure. Meanwhile, the luminescent properties of these nine coordination polymers in the solid state are also investigated. Especially the Eu and Tb compounds show bright red and green luminescence with luminescence lifetimes of 0.39 and 0.80 ms, respectively.     

Synthesis,crystal structures and cytotoxic activity of mononuclear nickel(II) and dinuclear zinc(II) complexes with ligand derived from S-benzyldithiocarbazate

Ni(L)₂ (1) and Zn₂(μ-OL)₂(L)₂ (2), (HL = S-benzyl-β-N-(2-bromobenzylidene) dithiocarbazate), were synthesized and characterized by elemental analysis and X-ray single-crystal diffraction analysis. 1 is a mononuclear neutral nickel(II) complex and the center nickel atom is chelated by donors of N₂S₂ possessing a distorted tetrahedral configuration, while in 2, the adjacent two complex molecules are linked through two O atoms to form a dimer and the center zinc atom is five-coordinate in a distorted trigonal–bipyramidal geometry. The cytotoxic activity study indicated that 2 showed potent cytotoxic activity against the human liver hepatocellular carcinoma (HepG2) cancer cell lines, with IC₅₀ 2.4 ± 0.2 μg·mL^− 1, which is slightly weaker than 5-fluoroacil (5-FU) (0.89 ± 0.21 μg·mL^− 1) as reference. A gel electrophoresis assay demonstrated the ability of the complex to cleave the pBR322 plasmid DNA.     

Effect of Gd doping on structural,optical properties,photoluminescence and electrical characteristics of CdS nanoparticles for optoelectronics

Synthesis of pure and 0.1 to 5?wt.% Gd-doped CdS nanoparticles (NPs) was achieved through a modified domestic microwave-assisted route in a short timespan at 700?W power. The formation of hexagonal CdS NPs was verified via X-ray diffraction analysis, and no structural variation was observed except for lattice variation. The size of the crystallites (D), dislocation concentration, and lattice strain were calculated, and the D was in the range of 3–6?nm. Fourier transform-Raman analysis confirmed the presence of 1LO, 2LO, and 3LO modes at 294.76, 590, and 890?cm^?1, respectively, in all the synthesized nanostructures, with minute variations in their positions due to doping; however, no new mode was observed. The position of the vibration modes was red shifted compared to that of the bulk material, indicating a confinement effect. Scanning electron microscopy (SEM) mapping/energy-dispersive X-ray spectroscopy revealed homogeneous doping of Gd and the presence of all the constituents in the final products. The morphology of the synthesized materials was tested via field-emission SEM, which revealed spherical NPs with small dimensions. Additionally, high-resolution transmission electron microscopy was performed to visualize the shape and size of the prepared 0.1% Gd:CdS NPs. The energy gap was calculated using the Kubelka–Munk theory and found to be in the range of 2.31–2.41?eV. The photoluminescence emission spectra exhibited two green emission peaks at 516?±?2?nm and 555?±?2?nm and showed the reduction of defects with Gd doping in terms of intensity quenching. The dielectric constant (${\epsilon }^{\text{'}}$), loss, and alternating-current electrical properties were studied in the high-frequency range. The values of ${\epsilon }^{\text{'}}$ were in the range of 17–27. An enhancement of these values was observed for CdS when it was doped with Gd. The electrical conductivity exhibited frequency power law behavior.     

Synthesis and properties of bis(sodium sulfonated ester) types of cleavable surfactants derived from 1-O-alkylglycerols

Novel sulfonated ester types of cleavable surfactants were easily prepared by acid-catalyzed esterification of 1-O-alkylglycerols with bromocarboxylic acids, followed by the Strecker reaction. These surfactants have good solubility in water. Though this series of cleavable surfactants are divalent in type, they show good micelle formation and the ability to lower surface tension. The solubility of these surfactants in hard water was more than 10 times higher than sodium 1-dodecanesulfonate. They decompose quickly and completely in 0.5 M NaOD. Their biodegradabilities were higher or almost the same as that of sodium 1-dodecanesulfonate.     

Two cobalt(II) coordination polymers based on carboxylate ligand: Preparation,crystal structures and magnetic properties

Two new coordination polymers, [Co₂(L)_1.5(OH)(H₂O)₂]·2H₂O (1) and [CoL(bpp)] (2) (H₂L = 2,5-dibenzoylterephthalic acid and bpp = 1,3-bis(4-pyridyl)propane), have been synthesized and characterized by elemental analyses, IR spectra, and thermogravimetric analyses. Their structures were determined by single crystal X-ray diffraction analyses. Complex 1 exhibits a 3D framework assembled from tetra-nuclear cobalt-oxygen bridged by carboxylic O atoms with a (4¹²·6³) topology. Complex 2 possesses a 2D layered structure which extends into a 3D architecture via C–H···π interaction between propane proton and the phenyl ring or pyridine ring of an adjacent sheets. Furthermore, the magnetic properties of them are discussed.     

Syntheses,structures and luminescence of zinc and cadmium coordination polymers with bis(1,2,4-triazol-1-yl)butane and benzenedicarboxylate

The self-assembly reactions of the flexible ligand 1,4-bis(1,2,4-triazol-1-yl)butane (btb) and rigid ligand 1,4-benzenedicarboxylate (bdc) with Zn(II) or Cd(II) give two novel coordination polymers {[Zn(bdc)(btb)](H₂O)₅}_n (1) and {[Cd₂(bdc)₂(btb)(H₂O)₂](H₂O)₇}_n (2). Coordination polymer 1, a supramolecular isomer of [Zn₂(bdc)₂(btb)₂](H₂O)₂ [X.L. Wang, C. Qin, E.B. Wang, Z.M. Su, Chem. Eur. J. 12 (2006) 2680], is a special 2D (6,3) network, with six Zn(II) atoms at six corners and four bdc and two double btb at six edges. Coordination polymer 2 exhibits a distorted 3D cubic topology that is built from dimer Cd₂ units. The blue luminescent emission maxima at 420 and 439 nm for 1, 440 and 455 nm for 2 were observed in the solid state at room temperature.