Novel soluble N-phenyl-carbazole-containing PPVs for light-emitting devices: Synthesis, electrochemical, optical, and electroluminescent properties

Novel PPV derivatives (PCA8-PV and PCA8-MEHPV) containing N-phenyl-carbazole units on the back-bone were successfully synthesized by the Wittig polycondensation of 3,6-bisformyl-N-(4-octyloxy-phenyl)carbazole with the corresponding tributyl phosphonium salts in good yields. The newly formed and dominant trans vinylene double bonds were confirmed by FT-IR and NMR spectroscopy. The polymers (with (M) over bar (w) of 6289 for PCA8-PV and 7387 for PCA8-MEHPV) were soluble in common organic solvents and displayed high thermal stability (T(g)s are 110.7 degreesC for PCA8-PV and 92.2 degreesC for PCA8-MEHPV, respectively) because of the incorporation of the N-phenyl-carbazole units. Cyclic voltammetry investigations (onsets: 0.8 V for PCA8-PV and 0.7 V for PCA8-MEHPV) suggested that the polymers possess enhanced hole injection/transport properties, which can be also attributed to the N-phenyl-carbazole units on the backbone. Both the single-layer and the double-layer light-emitting diodes (LEDs) that used the polymers as the active layer emitted a greenish-blue or bluish-green light (the maximum emissions located 494 nm for PCA8-PV and 507 nm for PCA8-MEHPV, respectively).

Blue light-emitting poly(fluorene-co-benzene) containing an oxadiazole moiety

A new kind of polyfluorene containing oxadiazole as the side chain was synthesized. The introduction of oxadiazole moiety as more bulky group prevents the aggregation and reduces the crystallinity of the polymers. Efficient intramolecular energy transfer from oxadiazole moiety to the conjugated backbone has been realized, leading to 70% improvement of photoluminescence quantum efficiency of the designed polymers. Compared with PAF, the PFOXD exhibits significant improvement in electroluminescence properties, with luminous efficiency of 0.8 cd/A and maximum luminance of 1800 cd/m(2).

Preparation and the investigation of its electrochemical and photoluminescent characteristics of organic-inorganic hybrid multilayers containing europium-substituted heteropolytung state

Photoluminescent multilayers were fabricated by layer-by-layer deposition between europium-substituted heteropolytungstate K-13 [Eu(SiW11O39)(2)].28H(2)O (denoted ESW) and a cationic polymer of quaternized poly(4-vinylpyridine) partially complexed with osmium bis(2,2'-bipyridine) (denoted as QPVP-Os) on glassy carbon and quartz substrates. The resulting photoluminescent organic-inorganic hybrid multilayers were characterized by electrochemical impedance spectroscopy, UV-Vis absorption spectrometry, cyclic voltammetry and photoluminescence spectra. Electrochemical impedance spectroscopy, UV-Vis absorption spectrometry and cyclic voltammetry results demonstrated that the multilayers were regular growth each layer adsorption. The photoluminescent properties of the films at room temperature were investigated to show the characteristic Eu3+ emission pattern of D-5(0) --> (7) F-j.

Poly(aryl ether)s containing ter- and pentafluorene pendants for efficient blue light emission

Four novel thermally stable poly(aryl ether)s, e.g., P3F, P5F, P2A3F, and P2A5K containing ter- or pentafluorene units in the side chains for efficient blue light emission have been designed and synthesized. All the polymers show the optical properties identical to the corresponding monomers and are amorphous with higher glass transition temperature (T-g) than their monomeric Counterparts. The polymer light-emitting diodes (PLEDs) were fabricated with the device structure of ITO/(PEDOT:PSS)/polymer/Ca/Al. The incorporation of diphenylamine group to oligofluorene terminals significantly reduces the hole-injection energy barrier in PLEDs. The devices based on P2A3F and P2A5F show the luminous efficiencies of 1.2 and 2.0 cd/A at a brightness of 300 cd/m(2) with the Commission Internationale de L'Eclairage (CIE) coordinates of (0.15, 0.13) and (0.19, 0.20), respectively. All these indicate that the high-performance light-emitting polymers can be synthesized with the traditional condensation polymerization through careful design of polymer structures.

Synthesis and characterization of blue-light-emitting poly(aryl ether)s containing oligofluorenes in the main chain

A series of blue light-emitting poly(aryl ether)s (PAEs) containing ter- or pentafluorenes in the main chain have been synthesized via nucleophilic substitution polycondensation reaction. The energy levels of the polymers were tuned by introducing hole-transporting triaryamine groups in the side chains and/or incorporating electron-transporting oxadiazole segments in the main chain. The optical properties of the polymers are dominantly determined by the well-defined oligofluorene segments, and therefore all polymers show high photoluminescence quantum yield. Differential scanning calorimeter (DSC) characterizations indicate that they are vitrified polymers with high glass transition temperature (up to 156 degrees C). The polymers comprising pentafluorenes exhibit electroluminescent properties equal to or better than fully conjugated fluorene homopolymers. With the device structure of ITO/PEDOT:PSS/polymer/Ca/Al, an external quantum efficiency of 1.4% along with Commission Internationale de L'Eclairage (CIE) coordinates of (0.17, 0.09) has

Synthesis and characterization of RGD peptide grafted poly(ethylene glycol)-b-poly(L-lactide)-b-poly(L-glutamic acid) triblock copolymer

Advances in tissue engineering require biofunctional scaffolds that can provide not only physical support for cells but also chemical and biological cues needed in forming functional tissues. To achieve this goal, a novel RGD peptide grafted poly(ethylene glycol)-b-poly(L-lactide)-b-poly(L-glutamic acid) (PEG-PLA-PGL/RGD) was synthesized in four steps (1) to prepare diblock copolymer PEG-PLA-OH and to convert its -OH end group into -NH2 (to obtain PEG-PLA-NH2), (2) to prepare triblock copolymer PEG-PLA-PBGL by ring-opening polymerization of NCA (N-carboxyanhydride) derived from benzyl glutamate with diblock copolymer PEG-PLA-NH2 as macroinitiator, (3) to remove the protective benzyl groups by catalytic hydrogenation of PEGPLA-PBGL to obtain PEG-PLA-PGL, and (4) to react RGD (arginine-glycine-(aspartic amide)) with the carboxyl groups of the PEG-PLA-PGL. The structures of PEG-PLA-PGL/RGD and its precursors were confirmed by H-1 NMR, FT-IR, amino acid analysis, and XPS analysis. Addition of 5 wt % PEG-PLA-PGL/RGD into a PLGA matrix significantly improved the surface wettability of the blend films and the adhesion and proliferation behavior of human chondrocytes and 3T3 cells on the blend films. Therefore, the novel RGD-grafted triblock copolymer is expected to find application in cell or tissue engineering.

Preparation of linear alpha-olefins to high-molecular weight polyethylenes using cationic alpha-diimine nickel(II) complexes containing chloro-substituted ligands

A series of alpha-diimine nickel(II) complexes containing chloro-substituted ligands, [(Ar)N=C(C10H6)C=N(Ar)]NiBr2 (4a, Ar = 2,3-C6H3Cl2; 4b, Ar = 2,4-C6H3Cl2; 4c, Ar = 2,5-C6H3Cl2; 4d, Ar = 2,6-C6H3Cl2; 4e, Ar = 2,4,6-C6H2Cl3) and [(Ar)N=C(C10H6)C=N(Ar)](2)NiBr2 (5a, Ar = 2,3-C6H3Cl2; 5b, Ar = 2,4-C6H3Cl2; 5c, Ar = 2,5-C6H3Cl2), have been synthesized and investigated as precatalysts for ethylene polymerization. In the presence of modified methylaluminoxane (MMAO) as a cocatalyst, these complexes are highly effective catalysts for the oligomerization or polymerization of ethylene under mild conditions. The catalyst activity and the properties of the products were strongly affected by the aryl-substituents of the ligands used. Depending on the catalyst structure, it is possible to obtain the products ranging from linear alpha-olefins to high-molecular weight polyethylenes.

Green electroluminescent polyfluorenes containing 1,8-naphthalimide moieties as color tuner

A series of copolymers (CNPFs) containing low-band-gap 1,8-naphthalimide moieties as color tuner was prepared by a Yamamoto coupling reaction of 2,7-dibromo-9,9-dioctylfluorene (DBF) and different amount of 4-(3,6-dibromocarbazol-9-yl)-N-(4'-tert-butyl-phenyl)-1,8-naphthalimide (Br-CN) (0.05-1 mol% feed ratio). The light emitting properties of the resulting copolymers showed a heavy dependence on the feed ratio. In photoluminescence (PL) studies, an efficient color tuning through the Forster energy transfer mechanism was revealed from blue to green as the increase of Br-CN content, while in electroluminescence (EL) studies, the color tuning was found to go through a charge trapping mechanism. It was found that by introduction of a very small amount of Br-CN (0.1-0.5 mol%) into polyfluorene, the emission color can be tuned from blue to pure green with Commission International de l'Echairage (CIE) coordinates being (0.21, 0.42) and (0.21, 0.48). A green emitting EL single-layer device based on CNPF containing 0.1 mol% of Br-CN showed good performances with a low turn-on voltage of 4.2 V, a brightness of 9104 cd/m(2), the maximum luminous efficiency of 2.74 cd/A and the maximum power efficiency of 1.51 lm/W.

Syntheses, structures and near-IR luminescent studies on ternary lanthanide (Er-III, Ho-III, Yb-III, Nd-III) complexes containing 4,4,5,5,6,6,6-heptafluoro-1-(2-thienyl)hexane-1,3-dionate

The ligand Hhfth [4,4,5,5,6,6,6-heptafluoro-1-(2-thienyl)hexane-1,3-dione], which contains a heptafluoropropyl group, has been used to synthesize several new ternary lanthanide complexes (Ln = Er, Ho, Yb, Nd) in which the synergistic ligand is 1,10-phenanthroline (phen) or 2,2'-bipyridine (bipy). The two series of complexes are [Ln(hfth)(3)phen] [abbreviated as (Ln)1, where Ln = Er, Ho, Yb] and [Ln(hfth)(3)bipy] [abbreviated as (Ln)2, where Ln = Er, Ho, Yb, Nd]. Members of the two series have been structurally characterized. The growth morphology, diffuse reflectance (DR) spectra, thermogravimetric analyses, and photophysical studies of these complexes are described in detail. After ligand-mediated excitation of the complexes, they all show the characteristic near-infrared (NIR) luminescence of the corresponding Ln(3+) ions (Ln = Er, Ho, Yb, Nd). This is attributed to efficient energy transfer from the ligands to the central Ln(3+) ions, i.e. an antenna effect. The heptafluorinated substituent in the main hfth sensitizer serves to reduce the degree of vibrational quenching. With these NIR-luminescent lanthanide complexes, the luminescent spectral region from 1300 to 1600 nm, which is of particular interest for telecommunication applications, can be covered completely.

Syntheses and crystal structures of four new organotin complexes with Schiff bases containing triazole

Four new organotin complexes, namely [(Bu2Sn)(2)O(EtO)(L1)](2) (1), [(Bu2Sn)(2)O(EtO)(L2)](2) (2), [(Bu2Sn)(2)O(EtO)(L-3)](2) (3) and [Ph3Sn(L4)]center dot 0.5H(2)O (4), were obtained by reactions of Bu2SnO and Ph3SnOH with 4-phenylideneamino-3-methyl-1,2,4-triazole-5-thione (HL1), 4-furfuralideneamino-3-methyl-1,2,4-triazole-5-thione (HL2), 4-(2-thienylideneamino)-3-ethyl-1,2,4-triazole-5-thione (HL3) and 4-(3,5-di-t-butylsalicylideneamino)-3-ethyl-1,2,4-triazole-5-thione (HL4). Compounds 1-4 were characterized by elemental analysis, IR spectra and their structures were determined by single-crystal X-ray diffraction methods. Complexes 1-3 show similar structures containing a Sn4O4 ladder skeleton in which each of the exo tin atoms is bonded to the N atom of a corresponding thione-form deprotonated ligand. Complex 4 shows a mononuclear structure in which the tin atom of triphenyltin group is coordinated by the S atom of a thiol-form L4(-) anion.

Biodegradable electrospun poly(L-lactide) fibers containing antibacterial silver nanoparticles

Biodegradable poly(L-lactide) (PLA) ultrafine fibers containing nanosilver particles were prepared via electrospinning. Morphology of the Ag/PLA fibers and distribution of the silver nanoparticles were characterized. The release of silver ions from the Ag/PLA fibers and their antibacterial activities were investigated. These fibers showed antibacterial activities (microorganism reduction) of 98.5% and 94.2% against Staphylococcus aureus and Escherichia coli, respectively, because of the presence of the silver nanoparticles.

Synthesis and characterization of novel polythiophenes containing poly(ethylene oxide) side chains

Thiophene copolymers and their derivatives with poly(ethylene oxide) side chains were synthesized. The starting monomers were 3-hexylthiophene and 2-(3-thienyl) ethanol with poly(ethylene oxide) grafted to the side chains. New functionalized polythiophenes were prepared by both chemical oxidation with FeCl3 and electropolymerization. The conjugating polymers were characterized. The structures of the polythiophene derivatives agreed with the design.

Syntheses and properties of polyimides derived from diamines containing 2,5-disubstituted pyridine group

A Series of novel homo- and copolyimides containing pyridine units were prepared from the heteroaromatic diamines, 2,5-bis (4-aminophenyl) pyridine and 2-(4aminophenyl)-5-aminopyridine, with pyromelltic dianhydride (PMDA), and 3,3',4,4'-biphenyl tertracarboxylic dianhydride (BPDA) via a conventional two-step thermal imidizaton method. The poly(amic acid) precursors have inherent viscosities of 1.60-9.64 dL/g (c = 0.5 g/dL in DMAC, 30 degrees C) and all of them can be cast and thermally converted into flexible and tough polyimide films. All of the polyimides show excellent thermal stability and mechanical properties. The polyimides have 10% weight loss temperature in the range of 548-598 degrees C in air. The glass transition temperatures of the PMDA-based samples are in the range of 395-438 degrees C, while the BPDA-based polyimides show two glass transition temperatures (T(g)1 and T(g)2), ranging from 268 to 353 degrees C and from 395 to 418 degrees C, respectively. The flexible films possess tensile modulus in the range of 3.42-6.39 GPa, strength in the range of 112-363 MPa and an elongation at break in the range of 1.2-69%. The strong reflection peaks in the wide-angle X-ray diffraction patterns indicate that the polyimides have a high packing density and crystallinity.