Supramolecular isomerism in zinc hydroxide coordination polymers with pyridine-2,4-dicarboxylic acid: Two polymorphs with centrosymmetric two-dimensional and acentric three-dimensional coordination networks

Reactions of Zn(BF4)(2) and pyridine-2,4-dicarboxylic acid (2,4-pydcH(2)) in the presence of 1,2-bis( 4-pyridyl) ethylene or 1,3-bis(4-pyridyl) propane under hydro(solvo) thermal conditions yielded two polymorphic metal-organic coordination polymers formulated as Zn-2(OH)(2)(2,4-pydc) (1 and 2). Polymorph 1 features a two-dimensional (2-D) layer-like structure that is constructed by 2,4-pydc ligands bridging between the Zn-OH-Zn double-chain units. Each single Zn-OH-Zn chain is composed of mu(2)-OH groups connecting trigonal bipyramidal and tetrahedral Zn centers. Polymorph 2 is a 3-D coordination polymer containing 2-D Zn-OH-Zn sheets that consist of mu(2)- and mu(3)-OH groups and trigonal bipyramidal Zn centers. The sheets are pillared by 2,4-pydc ligands to form an acentric structural architecture. 1 and 2 are rare examples that the two polymorphs exhibit a centrosymmetric 2-D coordination network and an acentric 3-D coordination network, respectively. The different structures lead to differences in photoluminescent properties and thermal stabilities for 1 and 2.

Luminescent supramolecular polymers: Cd2+-directed polymerization and properties

A family of supramolecular polymers was prepared via Cd2+-directed self-assembly polymerization of his (2,2':6',2 ''-terpyridine)-based ligand monomers, using oligofluorenes and triphenylamine as bridges under mild conditions. The polymers were fully characterized using thermogravimetric analysis, inherent viscosity, electrochemical measurements, UV-visible spectroscopy, photoluminescence (PL) and electroluminescence (EL). Polymers with oligofluorenes as spacers exhibited blue emission (434-442 nm) in dimethyl acetamide (DMAc) solution, while polymers with triphenylamine as spacer presented an emission peak at 494 nn in DMAc solution. Complexation polymerization of bis(2,2':6',2 ''-terpyridine)-based ligand monomers with cadmium(II) improved fluorescence quantum yields dramatically, and the film PL quantum yields of these polymers were about 0.38-0.54. Single-layer light-emitting diodes were fabricated with the configuration indium tin oxide (ITO)/polymer/Ca/Al; the EL showed green emission and the onset voltages of the devices were 8-11 V.

Evolution of the interfacial tension between polydisperse "immiscible" polymers in the absence and in the presence of a compatibilizer

The interfacial tension sigma between two polyisobutylenes (PIB) of dissimilar polydispersity and two polydisperse samples of poly(dimethylsiloxane) (PDMS) was measured as a function of time by means of a pendent drop apparatus at different temperatures ranging from 30 to 110 degreesC. In addition to three of the four possible binary blends, the time evolution of sigma was also determined for one ternary system, where the PIB phase contained 0.03 wt % of a diblock copolymer poly(isobutylene-b-dimethylsiloxane). The pronounced decrease of sigma with advancing time, observed in all cases, is attributed to the migration of the interfacially active lower molecular weight components of the homopolymers and of the compatibilizer into the interphase. Several days are normally required until a becomes constant. These time independent values are not considered as equilibrium data, but accredited to stationary states. A kinetic model is established for sigma(t), which enables a detailed investigation of the rates of transport of the different migrating species of average molar mass of M.

Synthesis and catalytic application of chiral 1, 1 '-binaphthyl polymers

The synthesis of a new type of polymers with main chain chirality based on BINOL skeleton is described. Titanium-BINOLate catalysts are easily generated from these polymers and applied to the asymmetric reaction of Et2Zn with benzaldehyde. The products are obtained in good yields with moderate enantioselectivities.

Amplified spontaneous emission and gain from optically pumped films of dye-doped polymers

The amplified spontaneous emission and gain characteristics of various fluorescent dyes, 2-(1,1-dimethylethyl)-6(2-(2,3,6,7-tetrahydro-1,1,7,7-tetramethyl-1H,5H-benzo[ij] quinolizin-9-1)ethenyl)-4H-pyran-4-ylidene) propanedinitrile (DCJTB) and 4-dicyanomethylene-2-methyl-6-(p-dimethyl-aminostyryl)-4H-pyran (DCM), doped in polystyrene (PS) matrices were studied and compared. It was found that DCJTB has a larger net gain, 40.72 cm(-1), a lower loss, 2.49 cm(-1), and a lower threshold, 0.16 (mJ/pulse)/cm(2), than DCM, which has a net gain of 11.95 cm(-1), a loss of 9.25 cm(-1), and a threshold of 4(mJ/pulse)/cm(2). The improvement of performance in DCJTB PS films is attributed to the larger free volume of DCJTB caused by the introduction of steric spacer groups into the DCJTB molecule.

Brittle-ductile transition of particle toughened polymers: influence of the matrix properties

It was theoretically pointed out that the product of the yield stress and yield strain of matrix polymer that determined the brittle-ductile transition (BDT) of particle toughened polymers. For given particle and test condition, the higher the product of the yield stress and the yield strain of the matrix polymer, the smaller the critical interparticle distance (IDc) of the blends was. This was why the IDc (0.15 mum) of the polypropylene (PP)/rubber blends was smaller than that (0.30 mum) of the nylon 66/rubber blends, and the IDc of the nylon 66/rubber blends was smaller than that (0.60 mum) of the high density polyethylene (HDPE)/rubber blends.

Cyclic oligomers of phenolphthalein polyarylene ether sulfone (ketone): Preparation through cyclo-depolymerisation of corresponding polymers

Cyclic oligomers of phenolphthalein polyarylene ether sulfone(ketone) were prepared through cyclo-depolymerisation of corresponding polymers using CsF as the catalyst in dipolar aprotic solvent DMAc and DMF, and a family of macrocycles containing from dimer up to at least heptamer were confirmed. by GPC, HPLC and MALDI-TOF-MS. The yields of cyclics get as high as 86.3% and 87.9% respectively.

Syntheses, crystal structures and properties of two Cu(II) coordination polymers: Cu(C3N2H4)(2)(HL)(2) andCU(C3N2H4)(2)L with C3N2H4 = imidazole, H2L = adipic acid

The reactions of freshly prepared Cu(OH)(2).xH(2)O and Cu(OH)(2-2y)(CO3)(y).zH(2)O precipitates with imidazole and adipic acid in CH3OH/H2O at pH = 5.4 yielded CU(C3N2H4)(2)(HL)(2) 1 and CU(C3N2H4)(2)L 2, respectively. Complex 1 consists of ribbon-like polymeric chains (1)(infinity)[CU(C3N2H4)(2)(HL)(4/2)], in which the octahedrally coordinated Cu atoms are doubly bridged by bis-monodentate hydrogen adipato ligands. The interchain N-H...O hydrogen bonding interactions are responsible for supramolecular assembly of the polymeric chains into open 3D frameworks and two-fold interpenetration of the resulting open frameworks completes the crystal structure of 1. Within complex 2, the Cu atoms are penta-coordinated to form CuN2O3 square pyramids and condensed into CU2N4O4 dimers, which are doubly bridged by twisted bis-monodentate adipato ligands into polymeric chains (1)(infinity)([CU(C3N2H4)(2)](2)L-4/2) with 4- and 18-membered rings progressing alternatively. The polymeric chains are assembled due to interchain N-H...O hydrogen bonding interactions. The thermal and magnetic behaviors of 1 and 2 is discussed.

Layer-by-layer electrodeposition of redox polymers and enzymes on screen-printed carbon electrodes for the preparation of reagentless biosensors

Layer-by-layer electrodeposition of redox polymer/enzyme composition films on screen-printed carbon electrodes for fabrication of reagentless enzyme biosensors has been proposed and the resulting films were found to be very stable and rigid.

Sulfonated poly(arylene-co-naphthalimide)s synthesized by copolymerization of primarily sulfonated monomer and fluorinated naphthalimide dichlorides as novel polymers for proton exchange membranes

A novel sulfonated aromatic dichloride monomer was successfully prepared by the reaction of 2, 5-dichlorobenzophenone with fuming sulfuric acid. Copolymerization of this monomer in the form of sodium salt (1) with N-(4-chloro-2-trifluoromethylphenyl)-5-chloro-1,8-naphthalimide (2) or bis(N-(4-chloro-2-trifluoromethylphenyl)1,4,5,8-naphthalimide (3) generated two series of novel poly(arylene-co-naphthalimide) s I-x and II-x where x represents the content of the sulfonated monomer. The synthesized copolymers with the -SO3H group in the side chains possessed high molecular weights revealed by their high viscosity and the formation of tough and flexible membranes. The copolymers exhibited excellent stability toward water and oxidation due to the introduction of the hydrophobic CF3 groups. The sulfonated copolyimides that incorporated with 1,8-naphthalimide (I-x) exhibited better hydrolytic and oxidative stabilities than those with 1,4,5,8-naphthalimide. Copolymer I-50 membrane endured for more than 83 h in Fenton's reagent at room temperature. The mechanical properties of I-50 membrane kept almost unchanged after immersing membrane in boiling water for 196 h. The proton conductivities of copolymer films increased with increasing IEC and temperature, reaching values above 6.8 x 10(-1) S/cm at 80 degrees C.

Syntheses, structures, and characterizations of four new silver(I) sulfonate coordination polymers with neutral ligands

In this paper, four novel silver(I) sulfonate coordination polymers containing neutral ligands, namely, [Ag(2)Ll (biim)(2)]center dot 2H(2)O (1). AgL2(biim) (2), [Ag(HL3)(Pic)(2)]center dot H2O (3), and [Ag-3(L3)(HL3)(4,4'-bipy)(3)(H2O)(2)]center dot 4H(2)O (4), have been synthesized [L1 = 3-carboxy-4-hydroxybenzenesulfonate, L2 = p-aminobenzenesulfonate, H(2)L3 = p-hydroxybenzenesulfonic acid, biim = 1,1'-(1.4-butanediyl)-bis(imidazole), Pic = beta-picoline, 4,4'-bipy = 4,4'-bipyridine]. For compounds 1 and 2, Ag(I) cations are bridged by biim ligands to form a one-dimensional (1D) "zigzag" chain, and L1 and L2 sulfonate ligands are not coordinated to the silver cation. Compound 3 has a dimeric structure in which two silver cations are bridged by two HL3 ligands. For compound 4, L3 ligand coordinates to a silver cation as a monodentate ligand, and Ag(l) cations are bridged by 4,4'-bipy ligands to form a ID chain. Compound 1 contains water dimers, while compound 4 contains water trimers. Compounds 1-3 display room-temperature photoluminescence.

Phenylene vinylene-based electroluminescent polymers with electron transport block in the main chain

We report a new route for the design of soluble phenylene vinylene (PV) based electroluminescent polymers bearing electron-deficient oxadizole (OXD) and triazole (TZ) moieties in the main chains with the aryloxy linkage. Both series of the PV-based polymers were prepared by Wittig reaction. By properly adjusting the OXD and/or TZ content through copolymerization, we can achieve an enhanced balance of hole- and electron injections, such that the device efficiency is significantly improved. Light-emitting diodes fabricated from P1, P2, P3, P4, P5, P6, and P7 with the configuration of Indium-Tin Oxide (ITO)/Poly (styrene sulfonic acid) doped poly (ethylenedioxythiophene) (PEDOT)/polymer/Ca/Al, emit bright green light with the maximum peak around 500 nm. For the device using the optimal polymer (P4) as emitting layer, a maximum brightness of 1300 cd/m(2) at 20 V and a maximum luminance efficiency of 0.325 cd/A can be obtained.

Two new Cu-II coordination polymers: Studies of topological networks and water clusters

Two new Cull coordination polymers, namely [Cu-2(BDC)(2)(L)(4)(H2O)(2)]center dot 14H(2)O (1) and [Cu-1.5(BTC)(L)(1.5)(H2O)(0.5)]center dot 2H(2)O (2), where L = 1,1'-(1,4-butanediyl)bis(imidazole), BDC = 1,4-benzene dicarboxylate, and BTC = 1,3,5-benzenetricarboxylate, have been synthesized at room temperature. Complex 1 exhibits an unusual, square-planar, four-connected 2D (2)(6)4 net, which has been predicated by Wells. Interestingly, three types of water clusters, namely (H2O)(6), (H2O)(8), and (H2O)(10), are observed in the hydrogen-bonded layers constructed by the BDC ligands and water molecules. The BTC anion in compound 2 is coordinated to the Cu" cation as tetradentate ligand to form a (6(6))(2)(4(2)6(4)8(4))(2)(6(4)810) net containing three kinds of nonequivalent points, Thermogravimetric analyses (TGA) and IR spectra for 1 and 2 are also discussed in detail.

Syntheses, crystal structures and magnetic properties of two heterometallic coordination polymers

Two heterometallic chain coordination polymers with the chemical formula {[Cu2Mn2L2(CH3OH)(H2O)] center dot 0.5CH(3)OH center dot 0.5CH(3)CH(2)OH}(n) (1) and {[Cu2Co2L2(H2O)(2)] center dot H2O}(n) (2) have been synthesized and characterized by IR, UV spectroscopy and single-crystal X-ray structural analysis, where H4L = 2-hydroxy-3-[(E)-({2-[(2-hydroxybetizoyl)amino]ethyl}imino)methyl] benzoic acid. Magnetic measurements showed that the two compounds exhibit antiferromagnetic coupling exchange interactions, and satisfactory fittings to the observed magnetic susceptibility data were obtained by assuming a linear four-spin arrangement with two isotropic magnetic exchange interactions.

Synthesis, characterization, properties and crystal structure of heterometallic 1D coordination polymers {[CuLZn center dot CuLZn(H2O)]center dot H2O}(n)

Copper-zinc heterometallic 1D chain coordination polymer has been synthesized and characterized by elemental analysis, and IR spectra etc. The crystal structure was determined by single-crystal X-ray diffraction analyses. The title complex is 1 D chain coordination polymer with the chemical formula {[CuLZn center dot CuLZn(H2O)]center dot H2O}(n), where H4L=N-(2-hydroxybenzamido)-N'-(3-carboxylsalicylidene)ethylenediamine. Its structural unit is comprosed of two tetranuclear cycles formed by two dissymmetrical tetranuclear units. These units polymerized each other to form 1 D chain coordination polymer.