Green light-emitting polyfluorenes with improved color purity incorporated with 4,7-diphenyl-2,1,3-benzothiadiazole moieties

By incorporating 4,7-diphenyl- 2,1,3 benzothiadiazole instead of 2,1,3-benzothiadiazole into the backbone of polyfluorene, we developed a novel series of green light- emitting polymers with much improved color purity. Compared with the state-of-the-art green light-emitting polymer, poly(fluorene-co-benzothiadiazole) (lambda max = 537 nm), the resulting polymers (lambda(max) = 521 nm) showed 10-20 nm blueshifted electroluminescence (EL) spectra and greatly improved color purity because the insertion of two phenylene units between the 2,1,3-benzothiadiazole unit and the fluorene unit reduced the effective conjugation length in the vicinity of the 2,1,3-benzothiadiazole unit. As a result, the resulting polymers emitted pure green light with CIE coordinates of (0.29, 0.63), which are very close to (0.26, 0.65) of standard green emission demanded by the National Television System Committee (NTSC). Moreover, the insertion of the phenylene unit did not affect the photoluminescence (PL) and EL efficiencies of the resulting polymers. PL quantum efficiency in solid films up to 0.82 was demonstrated. Single-layer devices (ITO/PEDOT/ polymer/Ca/Al) of these polymers exhibited a turn-on voltage of 4.2 V, luminous efficiency of 5.96 cd A(-1) and power efficiency of 2.21 lm W-1. High EL efficiencies and good color purities made these polymers very promising for display applications.

Crystal structures of EtEDTB center dot 1.4C(2)H(5)OH center dot 5H(2)O and H4EtEDTB(ClO4)(4)center dot C2H5OH (EtEDTB=N, N, N ', N '-tetrakis[2-(1-ethylbenzimidazolyl)methyl]-1,2-ethanediamine)

The crystal structures of EtEDTB.1.4C(2)H(5)OH.5H(2)O 1 and H4EtEDTB(ClO4)(4).C2H5OH 2 (EtEDTB = N, N,N',N'-tetrakis[2-(1-ethylbenzimidazolyl)methyl]-1,2-ethanediamine) have been determined by single-crystal X-ray diffraction method. Compound 1 crystallizes in the space group P(1) over bar with a = 11.489(2), b = 11.866(3), c = 12.002(3) Angstrom, alpha = 97.47(2), beta = 114.564(13), gamma = 114.11(2)degrees, V = 1266.6(5) Angstrom(3), Z = 1, M-r = 847.48, D-c = 1.111 g/cm(3), F(000) = 456 and mu(MoKalpha) = 0.076 mm(-1). A total of 5207 reflections were measured for 1, of which 4323 were independent. The structure of 1 was solved by direct methods and refined by full-matrix least-squares technique to the final R = 0.0706 and wR = 0.1802 for 1318 observed reflections with I > 2sigma(I). In the structure of 1, centrosymmetric EtEDTB molecules are linked by hydrogen bonds through water and ethanol to form 2-dimensional network. Compound 2 crystallizes in the space group C2/c with a = 24.260(5), b = 13.040(3), c = 17.680(4) Angstrom, beta = 97.50(3)degrees, V = 5545.2(2) Angstrom(3), Z = 4, M-r = 1140.80, D-c = 1.366 g/cm(3), F(000) = 2384 and mu(MoKalpha) = 0.289 mm(-1).

Polymerization of methyl methacrylate by iron(II) pyridinebisimine complexes

Fe(II) pyridinebisimine complexes activated with trialkylaluminium or modified methylaluminoxane (MMAO) as catalysts were employed for the polymerization of methyl methacrylate. Polymer yields, activities and polymer molecular weights as well as molecular weight distributions can be controlled over a wide range by the variation of the structures of the Fe(II) pyridinebisimine complexes and the reaction parameters such as Al/Fe molar ratio, monomer/catalyst molar ratio, monomer concentration, reaction temperature and time applied to the polymerization of methyl methacrylate. Under optimum condition, the catalytic activity of Fe(II) complex is of up to 74.5 kg(polym)/mol(Fe)h.

Synthesis of polysaccharide-stabilized gold and silver nanoparticles: a green method

A simple, green method was developed for the synthesis of gold and silver nanoparticles by using polysaccharides as reducing/stabilizing agents. The obtained positively charged chitosan-stabilized gold nanoparticles and negatively charged heparin-stabilized silver nanoparticles were characterized with UV-vis spectroscopy and transmission electron microscopy. The results illustrated the formation of gold and silver nanoparticles inside the nanoscopic polysaccharide templates. Moreover, the morphology and size distribution of prepared gold and silver nanoparticles varied with the concentration of both the polysaccharides and the precursor metal salts.

Highly efficient green-emitting phosphorescent iridium dendrimers based on carbazole dendrons

Green-emitting iridium dendrimers with rigid hole-transporting carbazole dendrons are designed, synthesized, and investigated. With second-generation dendrons, the photoluminescence quantum yield of the dendrimers is up to 87% in solution and 45% in a film. High-quality films of the dendrimers are fabricated by spin-coating, producing highly efficient. non-doped electrophosphorescent organic light-ernitting diodes (OLEDs). With a device structure of indium tin oxide/poly(3,4-ethylenedioxythiopheiie):poly(styrene sulfonic acid)/neat dendrimer/1,3,5-tris(2-N-phenylbenzimidazolyl)benzene/LiF/Al, a maximum external quantum efficiency (EQE) of 10.3% and a maximum luminous efficiency of 34.7 cd A(-1) are realized. By doping the dendrimers into a carbazole-based host, the maximum EQE can be further increased to 16.6%. The integration of rigid hole-transporting dendrons and phosphorescent complexes provides a new route to design highly efficient solution-processable dendrimers for OLED applications.

Highly efficient electroluminescence from green-light-emitting electrochemical cells based on Cu-I complexes

The complexes [Cu(dnpb)(DPEphos)](+)(X-) (dnpb and DPEphos are 2,9-di-n-butyl-1,10-phenanthroline and bis[2-(diphenyl-phosphino)phenyl]ether, respectively, and X- is BF4-, ClO4-, or PF6-) can form high quality films with photoluminescence quantum yields of up to 71 +/- 7%. Their electroluminescent properties are studied using the device-structure indium tin oxide (ITO)/complex/metal cathiode. The devices emit green light efficiently, with an emission maximum of 523 nm, and work in the mode of light-emitting electrochemical cells. The response time of the devices greatly depends on the driving voltage, the counterions, and the thickness of the complex film. After pre-biasing at 25 V for 40 s, the devices turn on instantly, with a turn-on voltage of ca. 2.9 V. A current efficiency of 56 cd A(-1) and an external quantum efficiency of 16% are realised with Al as the cathode. Using a low-work-function metal as the cathode can significantly enhance the brightness of the device almost without affecting the turn-on voltage and current efficiency. With a Ca cathode, a brightness of 150 cd m(-2) at 6 V and 4100 cd m(-2) at 25 V is demonstrated. The electroluminescent performance of these types of complexes is among the best so far for transition metal complexes with counterions.

Inverted to normal phase transition in solution-cast polystyrene-poly(methyl methacrylate) block copolymer thin films

We have investigated the inverted phase formation and the transition from inverted to normal phase for a cylinder-forming polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) diblock copolymer in solution-cast films with thickness about 300 nm during the process of the solution concentrating by slow solvent evaporation. The cast solvent is 1, 1,2,2-tetrachloroethane (Tetra-CE), a good solvent for both blocks but having preferential affinity for the minority PMMA block. During such solution concentrating process, the phase behavior was examined by freeze-drying the samples at different evaporation time, corresponding to at different block copolymer concentrations, phi. As phi increases from similar to 0.1 % (nu/nu), the phase structure evolved from the disordered sphere phase (DS), consisting of random arranged spheres with the majority PS block as I core and the minority PMMA block as a corona, to ordered inverted phases including inverted spheres (IS), inverted cylinders (IC), and inverted hexagonally perforated lamellae (IHPL) with the minority PMMA block comprising the continuum phase, and then to the lamellar (LAM) phase with alternate layers of the two blocks, and finally to the normal cylinder (NC) phase with the majority PS block comprising the continuum phase. The solvent nature and the copolymer solution concentration are shown to be mainly responsible for the inverted phase formation and the phase transition process.

Synthesis and structural characterization of beta-diketiminate-lanthanide Amides and their catalytic activity for the polymerization of methyl methacrylate and epsilon-caprolactone

The synthesis and catalytic activity of lanthanide monoamido complexes supported by a beta-diketiminate ligand are described. Donor solvents, such as DME, can cleave the chloro bridges of the dinuclear beta-diketiminate ytterbium dichloride {[(DIPPh)(2)nacnac]YbCl(mu-Cl)(3)Yb[(DIPPh)(2)nacnac](THF)} (1) [(DIPPh)(2)nacnac = N,N-diisopropylphenyl-2,4-pentanediimine anion] to produce the monomeric complex [(DIPPh)(2)nacnac]YbCl2(DME) (2) in high isolated yield. Complex 2 is a useful precursor for the synthesis of beta-diketiminate-ytterbium monoamido derivatives. Reaction of complex 2 with 1 equiv of LiNPr2i in THF at room temperature, after crystallization in THF/toluene mixed solvent, gave the anionic beta-diketiminate-ytterbium amido complex [(DIPPh)(2)nacnac]Yb(NPr2i)(mu-Cl)(2)Li(THF)(2) (3), while similar reaction of complex 2 with LiNPh2 produced the neutral complex [(DIPPh)(2)nacnac]Yb(NPh2)Cl(THF) (4). Recrystallization of complex 3 from toluene solution at elevated temperature led to the neutral beta-diketiminate-lanthanide amido complex [{(DIPPh)(2)nacnac}Yb(NPr2i)(mu-Cl)](2) (5). The reaction medium has a significant effect on the outcome of the reaction.

Highly efficient green light emitting polyfluorene incorporated with 4-diphenylamino-1,8-naphthalimide as green dopant

The dopant/host methodology, which enables efficient tuning of emission color and enhancement of the electroluminescence (EL) efficiency of organic light emitting diodes (OLEDs) based on small molecules, is applied to the design and synthesis of highly efficient green light emitting polymers. Highly efficient green light emitting polymers were obtained by covalently attaching just 0.3-1.0 mol% of a green dopant, 4-(N,N-diphenyl) amino-1,8-naphthaliniide (DPAN), to the pendant chain of polyfluorene (the host). The polymers emit green light and exhibit a high photoluminescence (PL) quantum yield of Lip to 0.96 in solid films, which is attributed to the energy transfer from the polyfluorene host to the DPAN dopant unit. Single layer devices (device configuration: ITO/PEDOT/Polymer/Ca/Al) of the polymers exhibit a turn on voltage of 4.8 V, luminance efficiency of 7.43 cd A(-1), power efficiency of 2.96 lm W-1 and CIE coordinates at (0.26, 0.58). The good device performance can be attributed to the energy transfer and charge trapping from the polyfluorene host to the DPAN dopant unit as well as the molecular dispersion of the dopant in the host.

Large-scale synthesis of Berlin green Fe[Fe(CN)(6)] microcubic crystals

Berlin green FeFe(CN)(6) microcubic crystals have been successfully prepared by a simple hydrothermal process between K-3[Fe(CN)(6)] with Na2S2O3 aqueous solution, free of any surfactant or template. The experimental results clearly show that the molar ratio of K-3[Fe(CN)(6)] to Na2S2O3 and their concentrations are the dominant processing factors in controlling the size, morphology, and composition of the resulting products.

Chitin and chitosan dissolved in ionic liquids as reversible sorbents of CO2

A novel dissolving process for chitin and chitosan has been developed by using the ionic liquid 1-butyl-3-methyl-imidazolium chloride ([Bmim]Cl) as a solvent, and a novel application of chitin and chitosan as substitutes for amino-functionalized synthetic polymers for capturing and releasing CO2 has also been exploited based on this processing strategy.

An effective approach to synthesis of poly(methyl methacrylate)/silica nanocomposites

A novel synthetic route for nearly monodispersed poly(methyl methacrylate)/SiO2 composite particles (PMSCP) is reported. Silica nanoparticles modified with oleic acid were used as 'seeds'. Methyl methacrylate (MMA) monomer was copolymerized with oleic acid via in situ emulsion polymerization, in the presence of an initiator; it resulted finally in the formation of composites with core-shell morphology. The composite particles were examined by transmission electron microscopy (TEM), scanning electron microscopy (SEM), x-ray photoelectron spectroscopy (XPS) and thermogravimetric analysis (TGA). The number of silica particles inside the composite particles increases with an increase in the silica concentration. The effect of grafted silica concentration on the morphology of PMSCP is also reported in detail. It was found by thermogravimetric analysis that PMSCP show a potential application for fire retardance.

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.

Nickel complexes catalyzed Heck reaction of iodobenzene and methyl acrylate

Nickel appears the most promising for the replacement of palladium among the inexpensive transition metals for that it is active for Heck reaction and about 500 times cheaper than palladium. In this article, we describe our recent results in the area of nickel-catalyzed Heck vinylations. Main focus is on the influence of ligand concentration in different organic solvents and the effects of the addition of water. The conversion is high in NMP and increases with increasing of PPh3/Ni ratio; in ethanol and toluene the conversion presents a maximum value on Ni(PPh3)(2). The effect of the addition of water is sensitive to the concentration of PPh3 and the nature of solvent, it was well explained with the formation and transfer of the active species in the different solvent systems.

Surface and interface morphology of polystyrene/poly(methyl methacrylate) thin-film blends and bilayers

The surface and interface morphologies of polystyrene (PS)/poly(methyl methacrylate) (PMMA) thin-film blends and bilayers were investigated by means of atomic force microscopy (AFM) and X-ray photoelectron spectroscopy. Spin-coating a drop of a PS solution directly onto a PMMA bottom layer from a common solvent for both polymers yielded lateral domains that exhibited a well-defined topographical structure. Two common solvents were used in this study. The structure of the films changed progressively as the concentration of the PS solution was varied. The formation of the blend morphology could be explained by the difference in the solubility of the two polymers in the solvent and the dewetting of PS-rich domains from the PMMA-rich phase. Films of the PS/PMMA blend and bilayer were annealed at temperatures above their glass-transition temperatures for up to 70 h. All samples investigated with AFM were covered with PS droplets of various size distributions. Moreover, we investigated the evolution of the annealed PS/PMMA thin-film blend and bilayer and gave a proper explanation for the formation of a relatively complicated interface inside a larger PS droplet.