Summary: Conjugated three‐ and four‐arm star polymers were successfully prepared by palladium catalyzed one‐pot Suzuki polycondensation of the multifunctional cores and an AB‐type monomer. The molecular weight of the star polymers could be controlled by the feed ratios of the monomers. The bromo end groups could be completely modified by fluorene mono boronic acid or triphenylamine mono boronic ester. The investigation of the optical, electrochemical, and thermal properties of the star polymers was also reported. All polymers exhibited good thermal stabilities and all the TPA‐capped polymers showed good hole‐transport abilities.
A series of conjugated copolymers of 9,9-dioctylfluorene and symmetrical pyrazine unit (BY) were synthesized by Suzuki copolymerization and were used as novel light-emitting materials in PLEDs.Efficient energy transfer was observed in both thin film and solution.Compared with the lowest occupied molecular orbital (LUMO) energy level of the polyfluorenes homopolymer (PFO),the lower LUMO energy levels of copolymers indicated that the introduction of the BY unit would be benefit to electron injection.The turn-... 相似文献
A homopolymer of 9,9′‐bis[4‐(2‐(2‐tetrahydropyranyloxy)ethoxy)phenyl]fluorene and its copolymers with 3,4‐benzothiadiazole and 4,7‐di(3(4‐n‐octylphenyl)‐2‐thienyl)‐2,1,3‐benzothiadiazole were synthesized to produce a series of thermally reactive blue, green, and red luminescent polymers. Thermolytic removal of the tetrahydropyran (THP) group from polymer films, rendered the films insoluble due to the formation of hydroxyl groups on the termini of side chains. Thermal removal of the THP was lowered by up to 200 °C, when acid is present in the films. These polymers were found applicable to patterning by NIR direct thermal lithography, in conjunction with a NIR dye and thermal acid generator. The presence of the phenyl groups at the 9‐site carbon was found necessary to eliminate fluorenone formation, and enhance the colour purity of the material.
Bipolar blue light-emitting polyfluorenes(PFSO-Cz) containing electron-deficient dibenzothiophene-S,S-dioxide(SO) and electron-rich carbazole(Cz) unit were synthesized. All the polymers show a high thermal stability with the decomposition temperatures over 400℃ and higher photoluminescence quantum yields. The highest occupied molecular orbital energy levels(EHOMO's) slightly enhance and the lowest unoccupied molecular orbital energy levels(ELUMO's) gently depress with the increase of Cz content in the polymers. PL spectra of the polymers display remarkable red shift and broadening with the increase of solvent polarities, indicating significant intramolecular charge transfer(ICT) effect in the polymers. Electroluminescence(EL) spectra of the polymers exhibit a broadening tendency with increasing the content of Cz unit in the polymers. The superior device performances were obtained with the maximum luminous efficiency(LEmax) of 5.2 cd/A, the maximum external quantum efficiency(EQEmax) of 4.8% and the Internationale de l'Eclairage(CIE)(x,y) coordinates of (0.16, 0.17) for PFSO15-Cz10 based on the single-layer device of ITO/PEDOT:PSS/EL/CsF/Al. The results indicate that the efficient bipolar blue light-emitting polyfluorenes are also constructed by Suzuki copolymerization using the monomers in common use. 相似文献
To investigate the role of oxygen defects on the photocatalytic activity of TiO2, the TiO2 nanocrystals with/without oxygen defects are successfully synthesized by the hydrothermal and sol-gel methods, respectively. The as-prepared TiO2 nanocrystals with defects are light blue and the absorption edge of light is towards the visible light region (~420 nm). Raman and X-ray photoelectron spectroscopy (XPS) measurements all confirm that the concentration of oxygen vacancies in the TiO2 synthesized by the sol-gel method is less than that synthesized through the hydrothermal route. The introduction of oxygen defects contributes to a new state in the band gap that narrows the band gap, which is the reason for the extension of light absorption into the visible light region. The photocurrent results confirm that this band-gap narrowing enhances the photocurrent response under simulated solar light irradiation. The TiO2 with oxygen defects shows a higher photocatalytic activity for decomposition of a methylene blue solution compared with that of the perfect TiO2 sample. The photocatalytic mechanism is discussed based on the density functional theory calculations and photoluminescence spectroscopy measurements. 相似文献
Novel water‐soluble dendronized fluorescent polyfluorenes (DFPFs) are prepared from hydrophilic monomers and hydrophobic comonomers. Incomplete energy transfer is found to result in a two‐color emission of the DFPFs at around 410 and 650 nm. The incomplete energy transfer can be attributed to the poor compatibility between the fluorene and benzothiadiazole units. Polyethylene oxide (PEO) encapsulation of the DFPFs shows over 90% cell viability, indicating good biocompatibility. These DFPFs show differential cellular uptake. P1 with fewer PEO chains exhibits limited cellular membrane uptake and low brightness in cells. By contrast, P3 with more PEO chains is efficiently internalized by cells and accumulated in the cytoplasm. A strong fluorescence from whole cells is also observed. 相似文献
Green light-emitting polyfluorenes containing 3,7-bis(4-hexylthiophen-2-yl)dibenzo[b,d]thiophene 5,5-dioxide(DHTSO)unit were synthesized.All the resulted polymers show high thermal stability with the decomposition temperatures(T_d)over 420°C and the glass transition temperatures(T_g)over 75°C.The polymers exhibit the enhanced highest occupied molecular orbital(HOMO)energy levels and the depressed lowest unoccupied molecular orbital(LUMO)energy levels with the increase of DHTSO unit in polymers.The photoluminescence(PL)spectra of the polymers show positive solvatochromism in solution with the variation of solution polarities,indicating remarkable intramolecular charge transfer(ICT)effect in the polymers containing DHTSO moiety.The fluorescence quantum yields((37)_(PL))are in the range of 34%-67%for PF-DHTSOs in film.All polymers possess two photon absorption(TPA)properties,and the TPA cross sections(?_2)are enhanced with increasing DHTSO unit in polymers.The highest?_2 is 2392 GM for PF-DHTSO15 in chloroform solution upon 740 nm excitation.The device of PF-DHTSO15 shows green emission with the Commission Internationale de L’.Eclairage(CIE)coordinates of(0.26,0.59),and the maximum luminous efficiency(LE_(max))of 10.8 cd·A~(-1) with the configuration of ITO/PEDOT:PSS/EL/Cs F/Al.These results indicate that introducing DHTSO unit into polyfluorene backbone could be a promising molecular design strategy for TPA and effective green-light emission. 相似文献
A polyfluorene 12 has been prepared in which bulky polyphenylene dendrimer substituents suppress formation of long wavelength emitting aggregates, thus giving a polymer with pure blue emission. Absorption- and emission spectra and molecular modeling confirm that the bulky dendrimer side chains do not cause extra torsion between the fluorene units. New polyfluorenes with 9,9-diaryl substituents have been prepared to determine the minimum size of substituent necessary for aggregation suppression. An LED using 12 has been demonstrated to produce blue emission with onset voltages below 4 V. 相似文献
Although it is well-known that nitroaromatic compounds quench the fluorescence of different conjugated polymers and form colored Meisenheimer complexes with proper nucleophiles, the potential of paper as a substrate for those macromolecules can be further developed. This work undertakes this task, impregnating paper strips with a fluorene-phenylene copolymer with quaternary ammonium groups, a bisfluorene-based cationic polyelectrolyte, and poly(2-(dimethylamino)ethyl methacrylate) (polyDMAEMA). Cationic groups make the aforementioned polyfluorenes attachable to paper, whose surface possesses a slightly negative charge and avoid interference from cationic quenchers. While conjugated polymers had their fluorescence quenched with nitroaromatic vapors in a non-selective way, polyDMAEMA-coated papers had a visual response that was selective to 2,4,6-trinitrotoluene (TNT), and that could be easily identified, and even quantified, under natural light. Far from implying that polyfluorenes should be ruled out, it must be taken into account that TNT-filled mines emit vapors from 2,4-dinitrotoluene (DNT) and dinitrobenzene isomers, which are more volatile than TNT itself. Atmospheres with only 790 ppbv TNT or 277 ppbv DNT were enough to trigger a distinguishable response, although the requirement for certain exposure times is an important limitation. 相似文献
In the present study, the interaction of serine (SER) amino acid (AA) with the pristine and defected carbon nanotubes (CNTs) has been investigated by employing the molecular dynamics (MD) and the density functional theory (DFT) approaches. Furthermore, the potential application of CNTs with and without the Stone-Wales (SW) defects in sensing of SER chirality has been studied. Our results confirm that introducing the chiral l and d SERs (LSER and DSER) exerts a significant effect on the electronic and optical properties of the CNTs with and without the SW defect. According to the MD results, it is observed that for all the structures, the obtained minimum distance is among the SER aliphatic segments and the tube atoms. The calculated structural and electronic properties of pristine and defected CNT are in good agreement with the reported research studies. The results indicate that pyramidalization angles (θp) at C atoms are altered in the presence of the SW defects. The overall increment of θp suggests that the reactivity has increased at the defective regions. In the case of CNT with one SW defect (CNTSW1), the central C–C bond of the SW defect is the most chemically reactive site. Our results establish that pristine CNT is a semiconductor when the LSER and DSER are adsorbed (with the band gap of 0.30 eV and 0.32 eV, respectively). The LSER-adsorbing CNT with two SW defects (CNTSW2) is a semiconductor with a reduced band gap (0.41 eV), while the DSER-adsorbing CNTSW2 is an n-type semiconductor (with a band gap of 0.70 eV). The optical properties are inferred from the dielectric functions of the CNTs. The most remarkable result belongs to the CNTSW2; the imaginary part of the CNTSW2 dielectric function can sensitively distinguish the chirality of the SER amino acid.