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1.
We report on circularly polarized light emitted from a chiral nematic liquid crystal doped with a luminescent organolanthanide dye. The organolanthanide emission displays an extremely narrow spectral bandwidth of ΔλE =8 nm. This is considerably narrower than the CNLC selective reflection bandwidth ΔλR =60 nm. When conventional dyes with broader emission bandwidths are dissolved into CNLCs, the average degree of circular polarization g of emitted light is reduced from the maximum degree g MAX ; this is due to the overlap of the emission band with the reflection band edges, and spectral regions outside the reflection band. Here, however, we can place the entire emission band inside the reflection band and achieve g ≈g MAX =1.27. Furthermore, a high degree of circular polarization is maintained under off-axis viewing up to a viewing angle of ≈30° to the normal.  相似文献   

2.
Two new soluble alternating carbazolevinylene‐based polymers POXD and PTPA as well as the corresponding model compounds MOXD and MTPA were synthesized by Heck coupling. POXD and MOXD contained 2,5‐diphenyloxadiazole segments, while PTPA and MTPA contained triphenylamine segments. All samples displayed high thermal stability. The polymers had higher glass transition temperature (Tg) than their corresponding model compounds. The samples showed absorption maximum at 364–403 nm with optical band gap of 2.62–2.82 eV. They emitted blue‐green light with photoluminescence (PL) emission maximum at 450–501 nm and PL quantum yields in THF solution of 0.15–0.36. The absorption and the PL emission maxima of PTPA and MTPA were blue‐shifted as compared to those of POXD and MOXD . The electroluminescence (EL) spectra of multilayered devices made using four materials exhibited bluish green emissions, which is well consistent with PL spectra. The EL devices made using poly(vinyl carbazole) doped with MOXD and MTPA as emitting materials showed luminances of 12.1 and 4.8 cd m?2. POXD and PTPA exhibited 25.4, and 96.3 cd m?2, respectively. The polymer containing the corresponding molecules in the repeating group showed much higher device performances. Additionally, POXD and MOXD exhibited better stability of external quantum efficiency (EQE) and luminous efficiency with current density resulting from enhancing the electron transporting properties. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5592–5603, 2008  相似文献   

3.
Copolyfluorenes PFG1~PFG4 slightly doped with 0.006–0.5 mol % of 2,5‐dihexyloxy‐1,4‐bis(2‐phenyl‐2‐cyanovinyl)benzene (green chromophore) were synthesized by the Suzuki coupling reaction to be evaluated as hosts for white‐light electroluminescent (EL) devices. Their optical, thermal and electrochemical properties were almost identical to those of polyfluorene ( PF ) due to minimal chromophore content. However, the electroluminescent (EL) spectra of the PFGn were very different from photoluminescence spectra in film state. Relative intensity of green emission (ca. 521 nm) in EL spectra are much stronger than those in PL spectra, which can be attributed to charges trapping in the chromophores due to its narrow band gap (Eg ≈ 2.56 eV). The performance of EL devices [ITO/PEDOT:PSS/polymer/Ca (50 nm)/Al (100 nm)] were improved with an increase in chromophore content. The PFG4 device revealed the best performance (6790 cd/m2, 1.69 cd/A), and the PFG1 and PFG2 devices exhibited comparable intensity in blue and green emissions. Blend EL devices were fabricated by using the PFGn as the hosts and a red iridium complex [Ir(piq)2(acac)] as dopant. By controlling the amount of the iridium complex, the white‐light emitting device was achieved with PFG2 , with maximum brightness and CIE coordinate being 4120 cd/m2 and (0.31, 0.28), respectively. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 149–160, 2009  相似文献   

4.
《Liquid crystals》1999,26(2):181-185
Circularly polarized photoluminescence (CPPL) was characterized for rod-like molecules of Exalite 428 helically arranged in a chiral-nematic liquid crystalline film. With an unpolarized excitation at 370nm, CPPL intensities measured at 428nm, and a selective reflection wavelength ranging from 7.2 to 72.6mum, the observed dissymmetry factor, g, was found to be in excellent agreement with theoretical prediction, without resorting to adjustable parameters. As a result, new insight into liquid crystal-induced CPPL has emerged. Specifically, it was found that circular dichroism and circular polarization of the excitation beam prior to inducing linearly polarized photoluminescence (LPPL) at quasi-nematic layers play an insignificant role. The relatively large g value in the spectral region far removed from the selective reflection band was attributed to the circular polarization of LPPL emanating from all quasi-nematic layers comprising the chiral-nematic film. In the absence of a fluorescent dye, the propagation of unpolarized light through the chiral-nematic film under otherwise identical conditions results in no circular polarization. The present study has provided a foundation for generating circularly polarized light by way of photo-excitation with unpolarized light of a chiral-nematic film containing a fluorescent dye. e e  相似文献   

5.
Highly efficient phosphor‐converted light‐emitting diodes (pc‐LEDs) are popular in lighting and high‐tech electronics applications. The main goals of present LED research are increasing light quality, preserving color point stability and reducing energy consumption. For those purposes excellent phosphors in all spectral regions are required. Here, we report on ultra‐narrow band blue emitting oxoberyllates AELi2[Be4O6]:Eu2+ (AE=Sr,Ba) exhibiting a rigid covalent network isotypic to the nitridoalumosilicate BaLi2[(Al2Si2)N6]:Eu2+. The oxoberyllates’ extremely small Stokes shift and unprecedented ultra‐narrow band blue emission with fwhm ≈25 nm (≈1200 cm?1) at λem=454–456 nm result from its rigid, highly condensed tetrahedra network. AELi2[Be4O6]:Eu2+ allows for using short‐wavelength blue LEDs (λem<440 nm) for efficient excitation of the ultra‐narrow band blue phosphor, for application in violet pumped white RGB phosphor LEDs with improved color point stability, excellent color rendering, and high energy efficiency.  相似文献   

6.
It is noteworthy that cholesteric liquid crystal (CLC) platforms have been witnessed in high-performance circularly polarized luminescence (CPL) behaviors through the highly organized chiral co-assembled arrangement of achiral dyes. However, most CPL-active design strategies are closely relative to the helix co-assembly structure of CLC rather than achiral dyes. Herein, we developed an intriguing regulation strategy for CPL-active CLC materials. They were regulated using the orientational order parameter (SF) of achiral dichroic dyes as an incisive probe for the order arrangement degree of achiral dyes in CLC media. The I-shaped phenothiazine derivative PHECN dye (SF=0.30) emitted a strong CPL signal (|glum|=0.47). In contrast, the T-shaped derivative (PHEBen) dye (SF=0.09) showed a weak circular polarization level (|glum|=0.07) at similar CLC textures. Most interestingly, this kind of dichroic PHECN dye with a higher SF could greatly improve the contrast ratio of CPL (Δglum=0.47) and emission intensity (ΔFL=46.0 %) at direct-current electric field compared with the T-shaped PHEBen (Δglum=0.07 and ΔFL=1.0 %) in CLC. This work demonstrates that an induced CPL emission can be mediated using achiral dichroic dye, which will open a new avenue for developing excellent CPL-active display materials.  相似文献   

7.
The chemical oxidative polymerization (OP) of 8-hydroxyquinoline (HQ) in an organic medium leaded to the formation of the C-2 and C-4 linking poly (8-hydroxyquinoline) (PHQ). The structure of PHQ was confirmed by UV-Vis, FT-IR, and 1H-NMR. The characterization of polymer was performed by TG-DTA, differential scanning calorimetry, dynamic mechanical analysis, dynamic light scattering, size exclusion chromatography, X-ray diffraction, cyclic voltammetry, atomic force microscope, photoluminescence and solubility tests. The fluorescence spectrum of PHQ exhibited an emission peak at approximately 525 nm in DMSO. Accordingly, it was found PHQ emitted green light whereas HQ emitted yellow light in DMSO solvent. Optical band gaps (Eg) of PHQ was calculated to be 3.31 eV. The electrical conductivities of iodine doped-PHQ and undoped-PHQ were measured with four-point probe technique. Magnetic particles was prepared by chemical precipitation of mixed Fe(II) and Fe(III) salts and modified with HQ by using an in situ chemical oxidation polymerization method in organic medium.  相似文献   

8.
A series of conjugated hyperbranched polymers, hyperbranched copolymers, and linear polymers containing 2‐pyran‐4‐ylidenemalononitrile (acceptor) and triphenylamine/fluorene (donor) units were synthesized and characterized by FTIR, 1H NMR, thermogravimetric analyses, differential scanning calorimetry, gel permeation chromatography, UV–visible, photoluminescence, and cyclic voltammetry measurements. All the polymers show red‐light emission in the range of 566–656 nm both in solution and in solid state. The quantum efficiency of the polymers was in the range of 56–82%. Among the six polymers synthesized, only polymers containing fluorene units show Tg and polymers based on triphenylamine not exhibit Tg. The band gap of these polymers were found to be reasonably low; hyperbranched copolymer containing fluorene unit shows lowest band gap of 2.18 eV due to the stabilization of LUMO energy level by the electron withdrawing ? CN groups. The thermal and solubility behavior of the polymers were found to be good. All the EL spectra of the devices (indium‐tin oxide/poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate)/polymer/2,9‐dimethyl‐4,7‐diphenyl‐1,10‐phenanthroline/tris(8‐hydroxyquinoline)aluminum)/LiF/Al) show red‐light emission, and the device fabricated with P3 and P4 shows maximum luminance and luminous efficiency of 4104 cd m?2 and 0.55 cd Å?1 and 3696 cd m?2 and 0.47 cd Å?1, respectively, indicates that they had the best carrier balance. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012  相似文献   

9.
A soluble cyano‐substituted poly[(1,3‐phenylene vinylene)‐alt‐(1,4‐phenylene vinylene)] derivative ( 9 ) was synthesized and characterized. Comparison between 9 and its model compound ( 10 ) showed that the chromophore in 9 remained to be well defined as a result of a π‐conjugation interruption at adjacent m‐phenylene units. The attachment of a cyano substituent only at the β position of the vinylene allowed the maximum electronic impact of the cyano group on the optical properties of the poly(p‐phenylene vinylene) material. At a low temperature (?108 or ?198 °C), the vibronic structures of 9 and 10 were partially resolved. The absorption and emission spectra of a film of 9 were less temperature‐dependent than those of a film of 10 , indicating that the former had a lower tendency to aggregate. A light‐emitting diode (LED) based on 9 emitted yellow light (λmax ≈ 578 nm) with an external quantum efficiency of 0.03%. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3149–3158, 2003  相似文献   

10.
Summary: Alkyne copolycyclomerizations of aromatic diynes 2,7‐bis(4‐ethynylphenylethynyl)‐9,9‐dihexylfluorene ( I ) and 1,4‐bis(4‐ethynylphenylethynyl)benzene ( II ) with an aliphatic monoyne 1‐dodecyne ( A ) were effected by CpCo(CO)2hv in THF, producing hyperbranched poly(aryleneethynylene)s ( 1 and 2 ) of high molecular weights ( up to 4.4 × 104 Da) in high isolation yields (up to 97%). The polymers possessed outstanding thermal stability and emitted strong deep blue light of ≈400 nm when their solutions were photoexcited. The polymers effectively limited the light of a 532 nm laser, with the performance of 2 being better than that of C60, a well‐known optical limiter, under similar linear transmittance.

The structure of hyperbranched poly(aryleneethynylene).  相似文献   


11.
Photo‐chemically tunable photonic band gap materials are prepared by infiltration of liquid crystal polymers having azobenzene groups into voids of SiO2 inverse opal films. Linearly polarized (LP) light irradiation results in transformation from a random to an anisotropic molecular orientation of azobenzene side chains in the voids of the SiO2 inverse opal film, leading to the reversible and stable shift of the reflection peak to longer wavelength more than 15 nm. To improve switching properties, we use copolymers of azobenzene monomer and tolane monomer, which have higher birefringence, as infiltration materials into the voids. The azobenzene‐tolane copolymers are found to show higher birefringence than azobenzene homopolymers by the LP light irradiation at higher temperature. Consequently, the reflection band of the SiO2 inverse opal film infiltrated with the azobenzene‐tolane copolymer can be shifted to longer wavelength region more than 55 nm by the irradiation of LP light. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1981–1990, 2009  相似文献   

12.
Three new poly(p‐phenylenevinylene)‐based polymers containing two 1,3,4‐oxadiazole moieties in the main chain per repeat unit were synthesized by Heck coupling. A single, double, or triple bond was introduced between the oxadiazoles to provide a means for modifying the polymer properties. The polymers were readily soluble in common organic solvents and showed Tg values lower than 50 °C. The color of the emissive light in both the solid state and the solution could be tuned by a change in the nature of the bond between the oxadiazole rings. The polymers emitted ultraviolet‐green light in solution with a photoluminescence (PL) emission maximum at 345–483 nm and blue‐green light at 458–542 nm in thin films. The PL quantum yields in solution were 0.36–0.43. The electrochemical properties are affected by the nature of the bond between the oxadiazoles as well. In polymers with a single bond between the oxadiazoles, a lower ionization potential was observed than in polymers with a double or triple bond. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3079–3090, 2005  相似文献   

13.
Five new materials based on pyrazole derivatives have been synthesized and characterized as organic light‐emitting devices. This report presents a novel approach to combine pyrazole with aromatic hydrocarbons via methylene. The formed molecules exhibited twisted structures, which resulted in high glass transition temperatures (Tg), which ranged from 83.0 to 101.1°C. They also had high optical band gaps (Eg); most of their optical band gaps are determined by the absorption edge technique as 3.43 to 3.66 eV, evaluated photophysical properties of these synthesized novel chromophores, the optical properties such as maximum absorption and emission wavelengths (λ; nm), molar extinction coefficients (ε; cm?1·M?1), Stokes' shifts (ΔλST; nm), and quantum yields (φF). These compounds exhibited intense absorption bonds between 230 and 350 nm, and the effect of solvent polarity on emission of these pyrazole derivatives was also studied. In addition, they showed blue fluorescence in different solvents and bathochromic shift with the increase in the solvent polarity.  相似文献   

14.
Cholesteric materials display unique optical properties which can be exploited in opto-electronic applications such as light emitting diodes. The key feature is the position of the wavelength of the emitted light relative to the one of the selective reflection band. We have synthesized a set of cellulose derivatives displaying the cholesteric phase with the aim to investigate the correlation between chemical structure and properties. Phase transition temperatures, the chain packing, the wavelength of selective reflection but also absorption and fluorescence spectra were investigated as a function of the degree of substitution (DS), the nature of lateral substituents, the composition of doped systems and blends of different cellulose derivatives. Investigated were furthermore the degree of circular polarization of the emitted light for guest–host systems and for cellulose systems with chromophores linked by covalent bonds to the cellulose backbone as well as their performance in light emitting diodes. The conclusion is that the optical properties can be accounted for on the basis of the model of a one-dimensional photonic crystal. The limiting factor with respect to opto-electronic applications is the poor control of the uniformity of the helix formation and orientation.  相似文献   

15.
Copper dodecanoate films prepared by emulsion method exhibit superhydrophobic property with water contact angle of 155° and sliding angle of <2°. The films have been characterised by using X‐ray diffraction, field emission scanning electron microscopy and Fourier transform infrared spectroscopy techniques. Surface microstructure of copper dodecanoate consists of numerous microscale papillas of about 6–12 µm in length with a diameter in the range of 360–700 nm. The superhydrophobicity of the films is due to their dual micronano surface morphology. The wetting behaviour of the film surface was studied by a simple water immersion test. The results show that copper dodecanoate film retained superhydrophobic property even after immersing in water for about 140 h. The optical absorption spectrum exhibits two broadbands centred at 388 and 630 nm that have been assigned to 2B1g2Eg and 2B1g2B2g transitions of Cu2+ ions, respectively. The electron paramagnetic resonance spectrum exhibits two resonance signals with effective g values at g|| ≈ 2.308 and g ≈ 2.071, which suggests that the unpaired electron occupies dx2–y2 orbital in the ground state. Copyright © 2011 John Wiley & Sons, Ltd.  相似文献   

16.
The complexes [Au3(dcmp)2][X]3 {dcmp=bis(dicyclohexylphosphinomethyl)cyclohexylphosphine; X=Cl? ( 1 ), ClO4? ( 2 ), OTf? ( 3 ), PF6? ( 4 ), SCN?( 5 )}, [Ag3(dcmp)2][ClO4]3 ( 6 ), and [Ag3(dcmp)2Cl2][ClO4] ( 7 ) were prepared and their structures were determined by X‐ray crystallography. Complexes 2 – 4 display a high‐energy emission band with λmax at 442–452 nm, whereas 1 and 5 display a low‐energy emission with λmax at 558–634 nm in both solid state and in dichloromethane at 298 K. The former is assigned to the 3[5dσ*6pσ] excited state of [Au3(dcmp)2]3+, whereas the latter is attributed to an exciplex formed between the 3[5dσ*6pσ] excited state of [Au3(dcmp)2]3+ and the counterions. In solid state, complex [Ag3(dcmp)2][ClO4]3 ( 6 ) displays an intense emission band at 375 nm with a Stokes shift of ≈7200 cm?1 from the 1[4dσ*→5pσ] absorption band at 295 nm. The 375 nm emission band is assigned to the emission directly from the 3[4dσ*5pσ] excited state of 6 . Density functional theory (DFT) calculations revealed that the absorption and emission energies are inversely proportional to the number of metal ions (n) in polynuclear AuI and AgI linear chain complexes without close metal???anion contacts. The emission energies are extrapolated to be 715 and 446 nm for the infinite linear AuI and AgI chains, respectively, at metal???metal distances of about 2.93–3.02 Å. A QM/MM calculation on the model [Au3(dcmp)2Cl2]+ system, with Au???Cl contacts of 2.90–3.10 Å, gave optimized Au???Au distances of 2.99–3.11 Å in its lowest triplet excited state and the emission energies were calculated to be at approximately 600–690 nm, which are assigned to a three‐coordinate AuI site with its spectroscopic properties affected by AuI???AuI interactions.  相似文献   

17.
New chiral binaphthyl‐containing polyfluorene (PF) derivatives, PFOH , PFMOM , and PFP , bearing different binaphthyl units ((S)‐2,2′‐bis(methoxymethoxy)‐1,1′‐binaphthyl for PFMOM , (S)‐1,1′‐binaphthyl‐2,2′‐diol for PFOH , and (S)‐2,2′‐bis(diphenylphosphinyl)‐1,1′‐binaphthyl for PFP ) in the backbone have been designed and synthesized through Pd‐catalyzed Suzuki polycondensation. Their properties have been investigated in detail by 1H NMR, 13C NMR, TGA, DSC, UV–vis, photoluminescence (in solutions, in thin films before and after annealing), and circular dichroism (CD) spectroscopic methods compared with poly(9,9‐dihexylfluorene‐2,7‐diyl) ( PF ). The resulting copolymers possessed excellent solubility in organic solvents and emitted strong blue light. The phosphine oxide‐containing copolymers PFP and PFMOM exhibited higher quantum yields and better thermal spectral stability in comparison with PF . All the copolymers exhibited obviously the linearly polarized photoluminescent properties both in solutions and in solid states. High emission polarization ratios (RPL) of PFP were observed with no obvious decrease upon thermal annealing. In addition, investigation of the CD spectroscopic properties of these copolymers in THF solutions indicated that the chirality of the binaphthyls could be transferred to the whole PF backbone. All these results demonstrated that introduction of the chiral binaphthyls, particularly BINAPO, into the backbone could effectively improve the performances of the copolymers. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011  相似文献   

18.
The absorption and emission spectra at room temperature and at 77 K are reported for the monomers and μ-oxo dimers of (OEP)Sc(III) and (TPP)Sc(III). [Here (OEP) is octaethylporphin and (TPP) is tetraphenylporphin.] Exciton coupling effects are strongest in the B(Soret) band of [(OEP)Sc]2O dimer: (i) The peak is blue shifted by 11 nm; (ii) the Soret band has a long red tail out to 480 mn; (iii) the fluorescence polarization shows a broad negativ band ≈ 440 nm. A vibronic exciton coupling model can roughly interpret the data if there is substantial and variable tilting of the ring planes. Exciton effects are weaker in the B(Soret) band of [(TPP)SC]2O, presumably because there is less tilting. The effect of dimer formation on the Q band of [(OEP)Scl2O is to red shift the band ≈ 420 cm?1 and to nearly double the Q(0,0) halfwidth; there is no change in fluorescence yield with dimerization. Presumably for Q bands exciton coupling is weaker than inhomogeneous broadening. Both the phosphorescence yield and triplet lifetime at 77 K drop by case23 in the dimer, showing faster radiationless decay.  相似文献   

19.
The modulus and glass transition temperature (Tg) of ultrathin films of polystyrene (PS) with different branching architectures are examined via surface wrinkling and the discontinuity in the thermal expansion as determined from spectroscopic ellipsometry, respectively. Branching of the PS is systematically varied using multifunctional monomers to create comb, centipede, and star architectures with similar molecular masses. The bulk‐like (thick film) Tg for these polymers is 103 ± 2 °C and independent of branching and all films thinner than 40 nm exhibit reductions in Tg. There are subtle differences between the architectures with reductions in Tg for linear (25 °C), centipede (40 °C), comb (9 °C), and 4 armed star (9 °C) PS for ≈ 5 nm films. Interestingly, the room temperature modulus of the thick films is dependent upon the chain architecture with the star and comb polymers being the most compliant (≈2 GPa) whereas the centipede PS is most rigid (≈4 GPa). The comb PS exhibits no thickness dependence in moduli, whereas all other PS architectures examined show a decrease in modulus as the film thickness is decreased below ~40 nm. We hypothesize that the chain conformation leads to the apparent susceptibility of the polymer to reductions in moduli in thin films. These results provide insight into potential origins for thickness dependent properties of polymer thin films. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012  相似文献   

20.
The lowering of temperature from ≈ 300 K to ≈ 10 K caused drastic changes in the spectral composition of the recombinational afterglow of N atoms: the glow due to the B3Πgν″ | A 3Σ+uν″ transition with ν′ = 12-9 (λ ≈ 580 nm and λ ≈ 540 nm) disappeared whereas levels with ν′ = 8-5 (λ ≈ 560 nm) appeared. This effect is exlained in terms of Campbell and Thrush's recombination luminescence model (emitting B 3Hg state populated by radiationless transition from the lower A 3Σ+u state of the N2 molecule).  相似文献   

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