Solution-processed, undoped, deep-blue organic light-emitting diodes based on starburst oligofluorenes with a planar triphenylamine core

A series of starburst oligomers (T1-T3) that contained a fully diarylmethene-bridged triphenylamine core and oligofluorene arms were designed and synthesized through Suzuki cross-coupling reactions. Their thermal, photophysical, and electrochemical properties were also investigated. These materials showed high glass transition, in the range of 123-129 °C, and good film-forming abilities. They displayed deep-blue emission both in solution and as thin films. Solution-processed devices based on these oligomers exhibited highly efficient deep-blue electroluminescence and the device performances were significantly enhanced with the extension of the oligofluorene arms. The double-layered device that contained T3 as an emitter showed a maximum current efficiency of 3.83 cd A(-1) and a maximum external quantum efficiency of 4.19% with CIE coordinates of (0.16, 0.09), which are among the highest values for undoped deep-blue OLEDs that are based on solution-processable starburst oligomers.     

Starburst triarylamine based dyes for efficient dye-sensitized solar cells

We report here on the synthesis and photophysical/electrochemical properties of a series of novel starburst triarylamine-based organic dyes (S1, S2, S3, and S4) as well as their application in dye-sensitized nanocrystalline TiO2 solar cells (DSSCs). For the four designed dyes, the starburst triarylamine group and the cyanoacetic acid take the role of electron donor and electron acceptor, respectively. It was found that the introduction of starburst triarylamine group to form the D-D-pi-A configuration brought about superior performance over the simple D-pi-A configuration, in terms of bathochromically extended absorption spectra, enhanced molar extinction coefficients and better thermo-stability. Moreover, the HOMO and LUMO energy levels tuning can be conveniently accomplished by alternating the donor moiety, which was confirmed by electrochemical measurements and theoretical calculations. The DSSCs based on the dye S4 showed the best photovoltaic performance: a maximum monochromatic incident photon-to-current conversion efficiency (IPCE) of 85%, a short-circuit photocurrent density (J(sc)) of 13.8 mA cm(-2), an open-circuit photovoltage (V(oc)) of 0.63 V, and a fill factor (ff) of 0.69, corresponding to an overall conversion efficiency of 6.02% under 100 mW cm(-2) irradiation. This work suggests that the dyes based on starburst triphenylamine donor are promising candidates for improvement of the performance of the DSSCs.     

Solution‐Processed,Undoped, Deep‐Blue Organic Light‐Emitting Diodes Based on Starburst Oligofluorenes with a Planar Triphenylamine Core

A series of starburst oligomers (T1–T3) that contained a fully diarylmethene‐bridged triphenylamine core and oligofluorene arms were designed and synthesized through Suzuki cross‐coupling reactions. Their thermal, photophysical, and electrochemical properties were also investigated. These materials showed high glass transition, in the range of 123–129 °C, and good film‐forming abilities. They displayed deep‐blue emission both in solution and as thin films. Solution‐processed devices based on these oligomers exhibited highly efficient deep‐blue electroluminescence and the device performances were significantly enhanced with the extension of the oligofluorene arms. The double‐layered device that contained T3 as an emitter showed a maximum current efficiency of 3.83 cd A^?1 and a maximum external quantum efficiency of 4.19 % with CIE coordinates of (0.16, 0.09), which are among the highest values for undoped deep‐blue OLEDs that are based on solution‐processable starburst oligomers.     

Synthesis and Characterization of Pyrene‐Centered Starburst Oligofluorenes

A series of starburst materials ( T1 – T3 ) based on a pyrene core with four oligofluorene arms of different length have been synthesized and characterized. The starburst materials show good film forming ability and sky blue fluorescence. Electroluminescent devices take on a stable blue emission and the device performance increases with an increase in arm length. The single‐layered device made of T3 has a maximum brightness of over 2 700 cd · m⁻² and a maximum current efficiency of 1.75 cd · A⁻¹, which is among the best in starburst material devices. The morphology of T1 – T3 has been studied by atomic force microscopy. The starburst oligofluorenes with different arm lengths show a distinctive texture, which indicates the size dependent morphology of the starburst materials.

     

Carbazole end‐capped pyrene starburst with enhanced electrochemical stability and device performance

Carbazole end‐capped starburst molecule based on pyrene core “4CzFP” was synthesized and characterized. The starburst material shows good film‐forming ability and bright blue fluorescence. In cyclic voltammetry test, 4CzFP shows a high highest occupied molecular orbital energy level of ?5.26 eV, indicating it has good hole‐injection ability. The material is quite stable under series of cyclic voltammetry scans, implying its good electrochemical stability. Single‐layered electroluminescent device takes on stable blue emission with a peak current efficiency of 0.84 cd/A. Double‐layered device by adding Poly(N‐vinylcarbazole) (PVK) as a hole‐injection layer does not show any improvement, indicating that 4CzFP could be efficiently used as the hole‐injection/light‐emitting layer. The device performance is largely improved by adding a thin TPBI electron‐injection/transporting layer. The peak efficiency reaches 3.28 cd/A and the maximum brightness is over 2200 cd/m². © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Synthesis and characterization of deep blue emitters from starburst carbazole/fluorene compounds

A series of well-defined, highly fluorescent starburst compounds with a carbazole core and oligo(2,7-fluorene ethynylene) arms have been synthesized by Sonogashira coupling reaction and fully characterized. These conjugated compounds exhibit good solubility, high thermal stability, and excellent fluorescence quantum yields (up to 0.99). The incorporation of carbazole core interrupted the main-chain conjugation and resulted in blue-shifted absorption and emission. Moreover, deep blue light has been approached from organic light-emitting diodes (OLEDs) adopting these compounds as emitting layer.     

Synthesis and properties of a star-shaped organic material with triphenylamine and N-vinyl carbazole units

A starburst triphenylamine cored N-vinyl carbazole (V-Cz) branched compound was designed and synthesized via optimized Heck reaction in a yield of 40-60%.Moderate yield came from decomposition of V-Cz and self-coupling of triiodo-triphenylamine. TCz-TPA adopts a highly twisted propeller conformation by molecular mechanical optimization.It is readily soluble for its highly twisted conformation.Transparent and pinhole free films could be easily fabricated by spin-coating for its starburst structure.It emits blue-greenish light in CH_2Cl_2 peaked at 460 nm with a narrow full-width at half-maximum (FWHM) of 65 nm.As compared, the absorption peaks of the spin-coated film blue shifted and emission peak red shifted to 510 nm with a FWHM of 96 nm.     

六-(ω-羟基丙基)肌醇醚及其衍生物的合成

本文报道六-(ω-羟基丙基)肌醇醚及其相应的四个新衍生物的合成. 它们可用于新型多分枝大分子-----Cascade分子的合成研究.     

Low potential of starburst six-arylamino compounds generating conducting polymers

N,N′,N″-tris [4-(phenylamino)-phenyl]-1,3,5-Benzenetriamine, composed of six arylamines with a starburst type, was oxidized electrochemically to yield an electrically conducting polymer film. The polymerization potential was lower than those of aniline and its derivatives. The lower shift was explained in terms of the redox interaction between the cation radical and the other arylamines through phenyl groups. The linear relation of the oxidation potential with the inverse of the number of redox sites was valid even for the starburst compounds. Contribution to the International Workshop on Electrochemistry of Electroactive Materials (WEEM-2006), Repino, Russia, 24–29 June, 2006.     

星形超支化聚酯的合成及其光固化

紫外光固化具有快速反应、室温操作、低能消耗和无溶剂少污染等优点,现正以日益增长的速度应用于涂层和粘合剂等领域。然而,常规的线形光固化齐聚体具有缠结的柔性分子链结构,其粘度随着分子量的增大而快速增加,故其可加工性和应用受到很大的限制。     

Synthesis and characterization of new pyrrolidinium based protic ionic liquids. Good and superionic liquids

New pyrrolidinium-cation-based protic acid ionic liquids (PILs) were prepared through a simple and atom-economic neutralization reactions between pyrrolidine and Br?nsted acids, HX, where X is NO 3 (-), HSO 4 (-), HCOO (-), CH 3COO (-) or CF 3COO (-) and CH 3(CH 2) 6COO (-). The thermal properties, densities, electrochemical windows, temperature dependency of dynamic viscosity and ionic conductivity were measured for these PILs. All protonated pyrrolidinium salts studied here were liquid at room temperature and possess a high ionic conductivity (up to 56 mS cm (-1)) at room temperature. Pyrrolidinium based PILs have a relatively low cost, a low toxicity and exhibit a large electrochemical window as compared to other protic ionic liquids (up 3 V). Obtained results allow us to classify them according to a classical Walden diagram and to determinate their "Fragility". Pyrrolidinium based PILs are good or superionic liquids and shows extremely fragility. They have wide applicable perspectives for fuel cell devices, thermal transfer fluids, and acid-catalyzed reaction media as replacements of conventional inorganic acids.     

Synthesis of New Functional Silicon-Based Condensation Polymers

A new class of photosensitive aromatic polymers containing disilane units was successfully synthesized from new disilane-based monomers such as 1,2-bis(diethylamino)tetramethyldisilane and 1,2-bis(p-aminophenyl)tetrarnethyldisilane. The disilane-contain-ing aramids and polyimides had glass transition temperatures above 190°C, and all the polymers were thermally stable up to 300°C in air. The polymers were photosensitive; their molecular weight decreased rapidly upon ultraviolet light irradiation. The photosensitive polymers, especially the soluble polyimides having diphenyl sulfone units, were potential candidates for positive working photoresist materials. New highly branched polysiloxane star-burst polymers were synthesized by a siloxane synthetic reaction starting from tris[(phenyldimethylsiloxy)dimethylsiloxy]methylsilane and bis[(phenyldimethylsiloxy)methylsiloxy]dimethylsilanol as the initial core (G0-Ph) and the building block, respectively. Thus, the first generation polymer G1-Ph, second generation polymer G2-Ph, and third generation polymer G3-Ph had 6, 12, and 24 phenylsilyl groups in their exterior layers. The formation of the siloxane-based starburst polymers were confirmed by means of ¹H-, ¹³C-, and ²⁹Si-NMR spectroscopy. These polysiloxane starburst polymers were suggested to have spherical structure. Some functionalized starburst polymers were further synthesized by the introduction of functional groups in their exterior layers. New silica-polyimide hybrid materials were prepared by the sol-gel process through the hydrolysis-condensation reactions of tetraethoxysilane in the presence of the polyamic acid (polyimide precursor) in dimethylacetamide, followed by heating at 270°C. The hybrid system having silica content up to 70 wt% had good quality films. The spherical silica particles were dispersed homogeneously in the polyimide matrix. With increasing silica content, the glass transition temperature and decomposition temperature, as well as the modulus of the hybrid films, increased, while the coefficient of thermal expansion decreased.     

Preparation of a ribonucleic acid-(polyamidoamine)-(zirconia-urea-formaldehyde resin) high-performance liquid affinity chromatographic stationary phase

A preparative method for a high-performance liquid affinity chromatographic (HPLAC) stationary phase is described. The 3- to 5-microm nonporous composite spherical microparticles of zirconia and urea-formaldehyde (UF) resin are synthesized through the reaction of zirconyl chloride with hexamethylene tetra-amine and urea, and then it is used as the matrix of the HPLAC stationary phase of which the diameter and structure are determined by scanning electron microscopy. In a methanol medium, the polyamidoamine (PAMAM) starburst dentritic spacer arms are linked with the imido-groups on the surface of the matrix by the Michael addition reaction with methyl acrylate and the amination reaction with ethylene diamine. After repeating these steps in triplets, amine-terminated dentritic spacer arms with a generation of 3 are obtained. The topological structure of the spacer arms is examined by solid-state 13C NMR. The Br-substituted ribonucleic acid (RNA) ligand is obtained by the reaction of liquid bromine with RNA and bonded to the dendritic spacer arms of the matrix in a solution of NaOH (pH 9-11). The binding capacity of RNA is measured by UV spectrophotometry. A new type of stationary phase--RNA-(PAMAM)-(zirconia-UF resin--for HPLAC, which possesses starburst dendritic spacer arms, is synthesized and used for the separation of biological macromolecules.     

一种新的D-π-A型异佛尔酮衍生物的合成及性质

通过Knoevenagel反应,合成了具有D-π-A结构的异佛尔酮衍生物（2-(3-(4-(双(2-(2-硝基苯氧基)乙基)氨基)苯乙烯基)-5,5-二甲基环-2-烯-1-亚基)丙二腈）,产率为80.7%,用红外光谱、核磁共振氢谱对化合物进行了表征。 初步研究了该化合物的光学和电化学性质及热稳定性,结果表明,该化合物有较好的光学性质和热稳定性。为寻找新的发光材料进行了有益的探索。     

Synthesis and characterization of polyaromatic compounds using tri(naphthyl)indium

A variety of polyaromatic compounds bearing 1- and 2-naphthyl groups were prepared from the reactions of corresponding halides with tri(1- and 2-naphthyl)indium in good to excellent yields. Thermal, photophysical and electrochemical behaviors of carbazoles having naphthyl groups were studied. They have shown to be promising host and hole transporting materials in organic electroluminescence due to their high thermal stability, electrochemical reversibility and wide band gap.     

Self-assembly of spherical colloidal silica along the [100] direction of the FCC lattice and geometric control of crystallite formation

Opalescent starburst patterns were formed on a convex surface by sedimenting colloidal silica spheres with a low silica volume fraction. The opalescent starburst patterns were also formed by the radial expansion of the meniscus when sedimented samples were slowly dried. The dependence of starburst formation on the rate of sedimentation and drying was experimentally investigated. Self-assembled opals fabricated from colloidal silica spheres grew vertically along the [100] direction of the face-centered cubic lattice. Elongated single-crystal crystallites nearly 1 cm wide and a few centimeters long formed in the curve at the bottom of an ordinary laboratory beaker from sedimenting 200- and 290-nm colloidal silica spheres. The elongated crystallites appear to be the result of an increased sedimentation rate, which creates favorable growth conditions. This is caused by the presence of the curve in the beaker and the spheres' inability to expand into the interior of the beaker before being sedimented. A narrowing of crystallites is shown to result from the competition between neighboring crystallites and large crystallites are shown to result from a lack of competition during their formation.     

8.0% Efficient all-polymer solar cells based on novel starburst polymer acceptors

The polymer N2200, with its π-conjugated backbone composed of alternating naphthalene diimide(NDI) and bithiophene(DT)units, has been widely used as an acceptor for all-polymer solar cells(all-PSCs) owing to its high electron mobility and suitable ionization potential and electron affinity. Here, we developed two naphthalene diimide derivatives by modifying the molecular geometry of N2200 through the incorporation of a truxene unit as the core and NDI-DTas the branches. These starburst polymers exhibited absorption spectra and molecular orbital energy levels that were comparable to N2200. These copolymers were paired with the wide-bandgap polymer donor PTz BI-O to fabricate all-polymer solar cells(all-PSCs), which displayed impressive power conversion efficiencies up to 8.00%. The improved photovoltaic performances of all-PSCs based on these newly developed starburst acceptors can be ascribed to the combination of increased charge carrier mobilities, reduced bimolecular recombination, and formation of more favorable film morphology. These findings demonstrate that the construction of starburst polymer acceptors is a feasible strategy for the fabrication of high-performance all-PSCs.     

Prolonged charge-separated states of starburst tetra(diphenylaminofluoreno)[60]fullerene adducts upon photoexcitation

Construction of starburst C60(>DPAF-C9)4 pentads was coupled with the use of highly fluorescent diphenylaminofluorene-C9 (DPAF-C9) addends as donor components in conjunction with the fullerene acceptor during single-photon excitation processes. High quantum yields (PhiCS) of charge-separation processes in the range 0.83-0.90 for C60(>DPAF-C9)n (n = 1, 2, or 4) were obtained in the formation of C60*-(>DPAF*+-C9)(>DPAF-C9)n-1 transient states. The lifetime of the radical ion-pairs (tauRIP) was found to be 900 ns for starburst C60(>DPAF-C9)4 (3) samples, which is 6-fold longer than that of the linear analogue C60(>DPAF-C9) (1), with a ca. 2 times increase of the charge-separation rate (kCS) compared to that of 1. These data implied the important role of sterically hindered DPAF-C9 pendants arranged in a starburst-like environment that encapsulates the central C60 core on extending the tauRIP. We interpreted the phenomena by the occurrence of intramolecular migration or exchange of electron or positive charge among multiple DPAF-C9 pendants of C60*-(>DPAF*+-C9)(>DPAF-C9)n-1, which gives an increased rate in charge generation and delayed charge recombination.     

New ionic liquids with tris(perfluoroalkyl)trifluorophosphate (FAP) anions

The synthesis of new ionic liquids with tris(perfluoroalkyl)trifluorophosphate (FAP) anions is described. The physico-chemical properties (conductivity, viscosity, electrochemical and thermal stability) of this new generation of ionic liquids (molten salts) are discussed. FAP-ionic liquids show an excellent hydrolytic stability, low viscosity and high electrochemical and thermal stability that makes them attractive for use in electrochemical devices and as a new media for application in modern technologies and chemical synthesis.     

Spectral, thermal and electrochemical characterization of novel homo-dinuclear complexes [M2(H3DTPA)(H2O)6]Cl2·xH2O (M=Cr2+, Mn2+, Co2+, Ni2+ or Cu2+)

The title complexes were prepared and characterized employing spectral (FAB-Mass, IR, electronic, (1)H and (13)C NMR), thermal and electrochemical techniques. Analytical and FAB-Mass data suggested a homo-dinuclear stoichiometry. IR and electronic ligand field spectral studies coupled with molecular model computations have indicated a distorted octahedral geometry where the ligand coordinates as a hexadentate dianionic [H(3)DTPA](2-)(H(5)DTPA=diethylenetriaminepentaacetic acid) moiety. The electrochemical redox properties and the antibacterial activities of the compounds were also investigated.