Hole-transporting polymers containing carbazol-3,9-diyl and 1,4-phenylene fragments in the main chain

New carbazole-based polymers, which contain various content of electro-active fragments in the main chain connected via alkylene spacers, have been synthesized by Ni(0)-catalyzed Yamamoto-type aryl-aryl coupling reactions. These compounds represent amorphous materials of high thermal stability with glass-transition temperatures of 139-151 degrees C and thermal decomposition starting at temperatures above 400 degrees C. UV-vis absorption and photoluminescence emission spectra of the materials confirmed that the conjugated segments in the macromolecules are rather short.

Topological Diversity of Coordination Polymers Containing the Rigid Terephthalate and a Flexible N,N'-Type Ligand: Interpenetration, Polyrotaxane, and Polythreading

Reactions of zinc(II) or cadmium(II) salts with terephthalic acid (H(2)tp) and 1,3-bis(4-pyridyl) propane (bpp) have afforded four coordination polymers at room temperature, [Zn(mu-tp)(mu-bpp)](n)center dot 2nH(2)O (1), [Cd-2(mu-tp)(2)(mu-bpp)(3)](n)center dot 2nH(2)O (2), [Cd(mu-tp)(mu-bpp)(H2O)](n)center dot nH(2)O (3), and [Cd-2(mu-tp)(mu-bpp)(2)(bpp)(2)Br-2](n) (4). Single-crystal X-ray diffraction has revealed interesting topological features for these compounds.

Blue electroluminescent polymers with dopant-host systems and molecular dispersion features: polyfluorene as the deep blue host and 1,8-naphthalimide derivative units as the light blue dopants

We developed a series of highly efficient blue electroluminescent polymers with dopant-host systems and molecular dispersion features by selecting 1,8-naphthalimide derivatives as the light blue emissive dopant units, choosing polyfluorene as the deep blue emissive polymer host and covalently attaching the dopant units to the side chain of the polymer host. The polymers' EL spectra exhibited both deep blue emission from the polymer host and light blue emission from the dopant units because of the energy transfer and charge trapping from the polymer host to the dopant units.

Highly efficient red electroluminescent polymers with dopant/host system and molecular dispersion feature: polyfluorene as the host and 2,1,3-benzothiadiazole derivatives as the red dopant

By selecting polyfluorene as the polymer host, choosing 2,1,3-benzothiadiazole derivative moieties as the red dopant units and covalently attaching 0.3 mol% of the dopant units to the side chain of the polymer host, we developed a novel series of red electroluminescent polymers of dopant/host system with molecular dispersion feature. Their EL spectra exhibited predominant red emission from the dopant units because of the energy transfer and charge trapping from the polymer backbone to the dopant units. The emission wavelength of the polymers could be tuned by modifying the chemical structures of the dopant units.

Synthesis and characterization of color-stable electroluminescent polymers: Poly(dinaphtho [1,2-a : 1 ',2 '-g]-s-indacene)s

Two new stepladder conjugated polymers, that is, poly(7,7,15,15-tetraoctyldinaphtho[1,2-a:1',2'-g]-s-indacene) (PONSI) and poly(7,7,15,15-tetra(4-octylphenyl)dinaphtho[1,2-a:1',2'-g]-s-indacene) (PANSI) with alkyl and aryl substituents, respectively, have been synthesized and characterized. In comparison with poly(indenofluorene)s, both polymers have extended conjugation at the direction perpendicular to the polymer backbone because of the introduction of naphthalene moieties. The emission color of the polymers in film state is strongly dependent on the substituents. While PONSI emits at a maximum of 463 nm, PANSI with the same backbone but aryl substituents displays dramatically redshifted emission with a maximum at 494 nm.

3-phenylethynyl phthalimide end-capped imide oligomers and the cured polymers

In the past decades, 4-phenylethynyl phthalic anhydride (4-PEPA) has been the most important endcapper used for thermoset polyimide. As the isomer of 4-PEPA, 3-phenylethynyl phthalic anhydride (3-PEPA) has attracted our interest. In this article, 3-PEPA was synthesized and a comparative study with 4-PEPA on curing temperature, curing rate, thermal and mechanical properties of oligomers and cured polymers was presented. The new phenylethynyl endcapped model compound, N-phenyl-3-phenylethynyl phthalimide, was synthesized and characterized.

SYNTHESIS AND CHARACTERIZATION OF HYPERBRANCHED VINYL POLYMERS FROM RAFT POLYMERIZATION OF AN ASYMMETRIC DIVINYL MONOMER

Hyperbranched vinyl polymers were prepared by reversible addition-fragmentation chain transfer ( RAFT) polymerization of a styrenic asymmetric divinyl monomer. This was achieved by using cumyl dithiobenzoate or S-dodecyl-S'-(alpha,alpha'-dimethyl-alpha ''-acetic acid) trithiocarbonate as the chain transfer agent, 1,1'-azobis(cyclohexanecarbonitrile) or thermal initiation as a source of radicals. Cross-linking was inhibited by a rapid RAFT-based equilibrium between active propagation chains and dormant species, and thus a hyperbranched polymer with a monomer conversion as high as 80% was obtained. The hyperbranched structure and properties of the resultant polymers were characterized by a combination of H-1-NMR spectroscopy and a triple detection size exclusion chromatography (TRI-SEC). The hyperbranched vinyl polymer has a broad molecular weight distributions and a low Mark-Houwink exponent alpha value compared with the linear counterpart.

Macrocycle-Terminated Core-Cross-Linked Star Polymers: Synthesis and Characterization

We have synthesized macrocyclic polystyrene- (PS-) terminated PS star polymers via a core-cross-linking approach in this work. A tadpole-shaped macrocyclic PS-linear-PS copolymer was synthesized at first via click chemistry and ATRP polymerization method. The "living" ATRP initiating chain-ends of the tadpole-shaped copolymers were linked together via ATRP polymerization with divinylbenzene to form a core-cross-linked macrocyclic star polymer. The number of arms attached to the macrocyclic star polymers was measured with NMR. and absolute molecular weights with gel permeation chromatography (GPC) with multiangle laser light scattering detector. These macrocyclic star polymers had a highly cross-linked core and many radiating arms. The shorter tadpole-shaped precursors caused core-cross-linked star polymers with higher molecular weights and more arm numbers. The macrocycle-terminated core-cross-linked star polymers showed two glass transition temperatures, one arising from the linear branches and another from the macrocycles.

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.

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.

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.

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.