Synthesis and luminescent properties of block copolymers based on polyfluorene and polytriphenylamine

For the preparation of block copolymers containing polyfluorene (PF) and hole transporting segment, PF homopolymers with diphenylamine terminals were synthesized by Suzuki coupling polymerization. The terminals of PF were converted to polytriphenylamine (PTPA) block by C–N coupling polymerization to give PTPA-block-PF-block-PTPA (PF-PTPA) triblock copolymers with different PTPA chain lengths. These polymers were soluble in common organic solvents and readily formed thin films by solution processing. All of the polymers exhibited similar UV absorption and PL emission properties both in chloroform solution and in film state. PF-PTPA block copolymers showed relatively high HOMO compared with that of PF by cyclic voltammetry. Compared with corresponding PF homopolymers, the EL devices based on PF-PTPA block copolymers showed higher luminance and current efficiency than those of PF homopolymers because of the improvement of hole injection by the introduction of PTPA segment.     

New light emitting materials: Alternating copolymers with hole transport and emitting chromophores

A new type of novel high‐efficiency light‐emitting nitrogen‐containing poly(phenylene vinylene) (PPV)‐related copolymers, which have hole‐transfer moieties such as triphenylamine (TPA) and conjugated aromatic units such as 4,4′‐biphenylene, 1,4‐phenylene, 2,5‐dimethyl‐1,4‐phenylene, 1,4‐ or 1,5‐naphthylene, and 9,10‐anthrylene, was designed and synthesized by the well‐known Wittig–Hornor reaction. The resulting alternating copolymers were highly soluble in common organic solvents. They can spin‐cast onto various substrates to give highly transparent homogeneous thin films without heat treatment. The introduction of TPA units in the PPV backbone improved processibility and limited the π‐conjugation length. Furthermore, the additional π‐electron delocalization between the lone‐paired electron in the nitrogen atom and π‐electrons in the conjugated units contributed to the improvement of the fluorescence quantum yields of these copolymers. All these alternating copolymers except TPA–PAV have high‐efficiency photoluminescence and they are very promising for light‐emitting diodes (LEDs). It is very promising that TPA–PAV will emit white light when used in LED device due to the broad emission spectra. The origin of the broad spectrum is contributed by the charge‐transfer complex formation, which can be proved by the absorption and emission spectra of TPA–PAV solutions. When the aromatic units were 1,4‐phenylene, 1,4‐ or 1,5‐naphthylene, 4,4′‐biphenylene, and 9,10‐anthrylene, respectively, with increase of the capability to accept electrons in aromatic units, the charge transfer from TPA to aromatic units occurred; consequently, the fluorescence quantum yield decreased. The introduction of the alkoxy‐substitute group on the aromatic units in the polymer backbone caused the red shift of the absorption and emission spectra of the copolymers due to the stronger delocalization of the π‐conjugated system. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 3351–3358, 1999     

Synthesis and properties of fluorenyl–pyridinyl alternatingcopolymers for light‐emitting diodes

A novel series of well‐defined alternating poly[2,7‐(9,9‐di(2‐ethylhexyl)fluorenyl)‐alt‐pyridinyl] (PDEHFP) copolymers were synthesized using palladium(0)‐catalyzed Suzuki coupling reaction in high yields. These polymers were characterized using ¹H NMR, UV‐visible and fluorescence spectroscopies, gel permeation chromatography, thermal analysis and cyclic voltammetry. The optical properties of the copolymers, including photoluminescence (PL) and electroluminescence (EL), were studied. The difference in linkage position of pyridinyl units in the polymer backbone has significant effects on the electronic and optical properties of polymers in solution and in film state. Meta‐linkage (3,5‐ and 2,6‐linkage) of pyridinyl units in the polymer backbone is more favorable for pure blue emission and prevention of aggregation of polymer chains. PDEHFPs with 2,6‐ and 3,5‐linkage of pyridinyl units have relatively high PL efficiency of 37 and 44% in the film state. In comparison with homopolymer PDEHF, the copolymers with pyridinyl units possess low lowest unoccupied molecular orbital energy levels for easy electron injection from a cathode. Strong EL is observed and light‐emitting diodes (LEDs) exhibit typical rectifying characteristics. The emission intensity starts to increase at around 12 V. The emission peak wavelengths of the polymers roughly coincide with those of PL. This series of fluorene–pyridine‐based alternating copolymers seem to be candidates for polymeric LEDs. © 2013 Society of Chemical Industry     

Synthesis and studies of blue light emitting polymers containing triphenylamine‐substituted fluorene and diphenylanthracene moiety

Photoluminescent (PL) polymers containing triphenylamine‐substituted fluorene and diphenylanthracene (DPA) units were synthesized by aromatic nucleophilic substitution reaction. The light emitting polymers (LEPs) contains hole‐transporting triphenylamine (TPA) groups at the C‐9 position of fluorene and DPA‐emitting segments in the main chain. The obtained polymers were soluble in various organic solvents and thermally stable. The synthesized polymers were successfully characterized by elemental analyses, FTIR and, ¹H NMR spectroscopy. The electrochemical measurements and optical properties of the polymers were also studied. The obtained polymers showed significant blue emission. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Luminescent supramolecular polymers: Cd2+‐directed polymerization and properties

A family of supramolecular polymers was prepared via Cd²⁺‐directed self‐assembly polymerization of bis(2,2′:6′,2″‐terpyridine)‐based ligand monomers, using oligofluorenes and triphenylamine as bridges under mild conditions. The polymers were fully characterized using thermogravimetric analysis, inherent viscosity, electrochemical measurements, UV‐visible spectroscopy, photoluminescence (PL) and electroluminescence (EL). Polymers with oligofluorenes as spacers exhibited blue emission (434–442 nm) in dimethyl acetamide (DMAc) solution, while polymers with triphenylamine as spacer presented an emission peak at 494 nm in DMAc solution. Complexation polymerization of bis(2,2′:6′,2″‐terpyridine)‐based ligand monomers with cadmium(II) improved fluorescence quantum yields dramatically, and the film PL quantum yields of these polymers were about 0.38–0.54. Single‐layer light‐emitting diodes were fabricated with the configuration indium tin oxide (ITO)/polymer/Ca/Al; the EL showed green emission and the onset voltages of the devices were 8–11 V. Copyright © 2006 Society of Chemical Industry     

New luminescent 1,2,4-triazole/thiophene alternating copolymers: Synthesis, characterization, and optical properties

New five-membered ring heteroaromatic copolymers composed of 1-alkyl-1H-1,2,4-triazole and thiophene or bithiophene units were prepared by palladium-catalyzed polycondensation. The copolymers were soluble in organic solvents, and showed number-average molecular weights of 6200-23,700 in the GPC analysis. NMR spectroscopy revealed that the copolymers had a regio-random molecular structure. The optical properties, as well as the electrochemical properties, of the copolymers in solutions and films were determined. The polymers exhibited blue photoluminescence (PL) with an emission peak at about 420 nm and quantum yields of 36-43% in solutions, and the PL peak shifted to 470-480 nm in films. X-ray diffraction data suggested that the polymers formed a π-stacked structure in solid state.     

Two photoluminescent polymers based on fluorene and 2,4,6‐triphenyl pyridine: Synthesis and electroluminescence

Two fluorene and triphenyl pyridine‐based linear and dendronized copolymers, P1 and P2 , were synthesized and fully characterized by ¹H‐NMR, ¹³C‐NMR, and matrix assistant laser desorption/ionization time‐of‐flight mass spectra, respectively. The absorption, photoluminescence (PL) behavior, and energy band gaps of P1 and P2 relative to those of polyfluorene end‐capped with benzene ( P0 ) were examined through UV–vis, photoluminescent spectra, and cyclic voltammetry. The UV–vis absorption and PL emission behavior of P0 and P1 were hardly affected by molecular architecture, while those of P2 were strongly correlated with the dendronized molecular frameworks. Cyclic voltammetry studies indicated the lower highest occupied molecular orbital energy level and wider band gap of P2 thin solid film relative to those of P0 and P1 . The new polymers were thermally stable up to 410°C. The better luminance and external quantum efficiencies of P1 relative to those of P0 in polymer light‐emitting diode (PLED) applications are due to improved electron injection, charge trapping and recombination at the pyridine sites. Through the experiments, it is found that the triphenyl pyridyl segments and excimers‐formation make pronounced contribution to long wavelength emission in P1 ‐based blue light‐emitting materials, and the analogous materials containing 2,4,6‐triphenyl pyridyl unit of P1 constitute highly attractive materials for white PLED applications. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Novel blue‐light‐emitting polymers based on a diphenylanthracene moiety

New luminescent copolyethers with diphenylanthracene‐emitting segments and electron‐transporting benzoxazole phenyl were successfully synthesized by aromatic nucleophilic substitution. The polymers, characterized by NMR and IR spectroscopy, were obtained in high yields, showed good solubility in various organic solvents, and had high thermal stability with high glass‐transition temperatures (125–129). The number‐average molecular weights of the polymers were 10,000–20,000, and they had polydispersity indices of 1.2–1.4. The optical and electrochemical properties of the polymers were also investigated. The pure blue emission for the polymers (maximum wavelength = 430–440 nm) was obtained with high photoluminescence quantum efficiency (76–78%) in a chloroform solution. The blue electroluminescence for the poly(TDPB) (maximum wavelength = 440 nm) was obtained with a turn‐on voltage of 15–20 V when simple light‐emitting diodes (indium tin oxide/polymer/Al) were fabricated. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2151–2157, 2006     

A study of light‐emitting diodes constructed with copolymers having cyclohexyl thiophene and hexyl thiophene units

We report visible light emission from a diode made from copolymers of 3‐alkylthiophenes. These chemically synthesized copolymers exhibit improved electroluminescence and quantum efficiencies compared to poly (3‐cyclohexylthiophene). Good solubility of copolymers allows the fabrication of the light emitting diodes by spin‐cast polymer film. The devices emit greenish‐blue light in wavelength region of 550–580 nm, which is easily visible in poorly lighted room. The quantum efficiencies are in the range of 0.002 to 0.01% (photons per electron) at room temperature; which are significantly higher than corresponding values for poly(3‐cyclohexylthiophene) based light emitting diodes. The charge carrier mobility in the device is found to be 5.6 × 10⁻⁴ cm²/Vs. ©2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1051–1055, 2000     

Substituent effect on the optoelectronic properties of poly(p‐phenylenevinylene) based conjugated‐nonconjugated copolymers

Two classes of light emitting Poly(p‐phenylenevinylene) (PPV) based conjugated‐nonconjugated copolymers (CNCPs) have been synthesized. The conjugated chromophores containing 2‐methoxy‐5‐(2′‐ethylhexyloxy)‐1,4‐phenylenevinylene (MEHPV) and 2,5‐dimethyl‐1,4‐phenylenevinylene (DMPV) moieties are rigid segments and nonconjugated portion containing hexyl units are flexible in nature. All copolymers were synthesized by well‐known Wittig reaction between the appropriate bisphosphonium salts and the dialdehyde monomers. The resulting polymers were found to be readily soluble in common organic solvents like chloroform, THF and chlorobenzene. The effect of chromophore substituents on the optical and redox properties of the copolymers has been investigated. Color tuning was carried out by varying the molar percentage of the comonomers. The UV‐Vis absorption and PL emission of the copolymers were in the range 314–395 nm and 494–536 nm respectively. All the polymers show good thermal stability. Polymer light‐emitting diodes (PLEDs) were fabricated in ITO/PEDOT:PSS/emitting polymer/cathode configurations of selected polymers using double‐layer, LiF/Al cathode structure. The emission maxima of the polymers were around 499–536 nm, which is a blue‐green part of the color spectrum. The threshold voltages of the EL polymers were in the range of 5.4–6.2 V. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Preparation and characterization of alternating copolymers containing fluorene and hexyl‐ or perfluorohexyl‐substituted thiophene

Alternating copolymers containing fluorene and hexyl‐ or perfluorohexyl‐substituted thiophene were synthesized by a palladium‐catalyzed cross‐coupling reaction, and the structures of the polymers were confirmed using nuclear magnetic resonance spectroscopy. The absorption spectra of polymers containing perfluorohexyl substituents show shorter maximum wavelength due to the steric hindrance between fluorene and substituted thiophene units. In addition, the perfluorohexyl substituents can effectively interrupt the conjugation length of the polymers, which leads to an increase in the optical bandgap and decrease in the photoluminescence quantum yield. Solid‐state UV‐visible absorption and emission maxima of the polymers containing perfluorohexyl‐substituted thiophene units are blue‐shifted in comparison to those of polymers in solution due to the packing structure of perfluoroalkyl chains. © 2014 Society of Chemical Industry     

A highly soluble blue light emitting copolymer of anthracene and dialkyloxyl benzene prepared by oxidative-coupling reaction

A new kind of soluble copolymers incorporated anthracene and dialkyloxyl benzene moieties into main chain have been prepared by oxidative-coupling copolymerization. They were characterized by FT-IR, ¹H NMR, UV-Vis, GPC, X-ray, thermogrametric analysis and fluorescence spectroscopy. The copolymers are amorphous and show excellent solubility in common organic solvents, such as chloroform. Thermogrametric analysis of the copolymers revealed that they have good stability with the onset decomposition temperature above 330 °C. The fluorescence spectra of the copolymers in solid state film display blue light emitting properties with the maximum at 468 nm.     

New soluble rigid rod copolymers comprising alternating 2-amino-pyrimidine and phenylene repeat units: Syntheses, characterization, optical and electrochemical properties

A new type - π-conjugated copolymers of 2-amino-pyrimidine was prepared between 2-amino-4,6-diiodidepyrimidine and 1,4-dibromo-2,5-dialkoxybenzene by Sonogashira polycondensation. The structures of the copolymers were elucidated by FT-IR, ¹H NMR and ¹³C NMR, fluorescence spectroscopy, gel permeation chromatography, thermal analysis and element analysis. The derived polymers were soluble in common organic solvents and trifloroacetic acid and exhibited good thermal stability. They emitted green light under UV irradiation in solid state and blue or green light in solution phase, respectively. Electrochemical behavior of these new polymers depicted facile p-doping and good electron-transporting properties. These polymers displayed bathochromic shift when protonated with CH₃SO₃H acid in chloroform solutions or m-cresol solutions and the red-shifted peaks were observed from 490 nm to 652 nm. XRD patterns of copolymers showed that the intensity of peaks was enhanced with increasing alkyloxy chain length.     

Studies on the synthesis and optical properties of novel blue light‐emitting polymers containing phosphorus and oxadiazole structures

Novel phosphorus‐containing polymers with high‐electron‐affinity oxadiazole were synthesized and characterized by thermal analysis and spectroscopy (infrared, ultraviolet‐visible, photoluminescence, cyclic voltammetry) measurements. These new polymers can be used as blue electroluminescent materials and as electron‐transport layers in polymer light‐emitting diodes. In this study, aromatic polyethers containing electron‐transporting chromophores and emission chromophores were synthesized from 2,5‐bis‐(4‐fluoroaryl)‐1,3,4‐oxadiazole and 2‐(6‐oxido‐6H‐dibenz<c,e><1,2> oxaphosphorin‐6‐yl)‐1,4‐naphthalenediol (DOPO‐NBQ). The effects of reaction temperature and time on the formation of polyethers were investigated to obtain optimum conditions for polyether manufacturing. All the resulting polymers were thermally stable at <460 °C. The absorption peaks of these polymers were at 350–365 nm, whereas the photoluminescent peaks were at 460–481 nm. But, the intensity of polymer absorption decreased and a blue shift was observed in the photoluminescent spectra as the temperature increased. In addition, these polymers containing the electron‐transporting oxadiazole indeed showed extra reduction potentials in cyclic voltammetry measurements. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2367–2376, 2002     

Synthesis and properties of photoluminescent copolymer containing 1,3,4‐oxadiazole and carbazole rings

The luminescent copolymer 2‐phenyl‐5‐[3′‐(methacrylamido)phenyl]‐1,3,4‐oxadiazole and vinylcarbazole (PMAPO–VCZ), combining hole‐facilitating moiety, carbazole ring, and electron‐facilitating moiety, 1,3,4‐oxadiazole, as side groups, was synthesized by a radical polymerization of the olefinic monomer PMAPO and VCZ. For comparison, the homopolymer P‐PMAPO was also synthesized by similar procedures. The solubility, thermal, and optical properties of the copolymers were investigated. The synthesized copolymer was soluble in common organic solvents but the homopolymer of PMAPO was dissolved only by hot THF. Thermogravimetric analysis and differential scanning calorimetry measurements showed that the copolymer and homopolymer exhibit good thermal stability up to 360 and 340°C with glass‐transition temperatures higher than 105 and 65°C, respectively. The photoluminescence properties were investigated. The results showed that the copolymer emits blue and blue‐green light and the emission spectra of monomer and polymers exhibit obvious solvent effect. With the increase of polarity of solvents, the fluorescence spectra distinctly change, appearing with a red shift at room temperature. The concentration‐dependent emission spectra change significantly with the increase of concentration. In addition, when N,N‐dimethylaniline (DMA) was gradually added to the solution of copolymers, the emission intensity of fluorescence was dramatically increased. However, when the concentration of DMA was increased beyond a certain level, the emission intensity of fluorescence gradually decreased. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2777–2783, 2004     

Syntheses, characterization, and energy transfer properties of benzothiadiazole-based hyperbranched polyfluorenes

A series of benzothiadiazole-based (BT) hyperbranched polyfluorene copolymers with various branching degrees (5-40%) were designed and synthesized. TGA and film annealing tests showed the substantial thermal stability of these highly branched polymers. The optical performance of the polymers in solutions and as films, and their electrochemical properties were characterized. The energy transfer (ET) processes in these hyperbranched conjugated polymers, both in solutions and in the solid state, were also investigated. With the change of the solution concentration and the branching degree, the energy transfer efficiency of the polymers varied in solutions and the main photoluminescence (PL) peaks changed from blue to green region. As films, only green light emitted from BT units. In addition, the PL efficiency of the films decreased dramatically with the increase of branching degrees. All these features demonstrated that highly branched structure would effectively impede the intra- and interchain energy migration, especially in solutions, and remarkably influence the ET process in the solid state, which resulted in low PL efficiency.     

Synthesis and properties of liquid‐ crystalline triblock copolymers by ATRP,having electron‐transporting thiadiazole unit

ABA‐type block copolymers composed of 2,5‐diphenyl‐1,3,4‐thiadiazole (DPTD) oligoester and poly(methyl methacrylate) (PMMA) segments (M_n = 16 200 and 23 000) were synthesized by atom‐transfer radical polymerization and their liquid‐crystalline (LC) and photoluminescence (PL) properties were examined. The structures of block copolymers were identified by Fourier transform infrared and ¹H NMR spectroscopies. Differential scanning calorimetry measurement, polarizing microscopy observation and wide‐angle X‐ray analysis revealed that the block copolymers form thermotropic LC phase (smectic C) independent of molecular weights of PMMA segments, but a model polymer (PMMA segments having the DPTD unit in the central part) has no LC melt. Solution and solid‐state PL spectra indicated that all the block copolymers display blue emission arising from the DPTD unit. Their quantum yields are 17–21%, which increase with the PMMA chain lengths. The block copolymers have good aligned structures in the LC states, but their order parameter (S) values in sheared LC states were lower than those in the sheared LC compounds. The PL properties in the LC states were independent of the LC aligned structures. Cyclic voltammetry measurements showed that these block copolymers have deep HOMO levels compared with polymers composed of oxadiazole rings. Copyright © 2007 Society of Chemical Industry     

Blue light‐emitting poly(p‐phenylenevinylene) derivative with oxadiazole and carbazole pendant groups

A blue light‐emitting statistical poly(p‐phenylenevinylene) (PPV) copolymer with hole‐transporting carbazole and electron‐transporting oxadiazole pendant groups attached to the kinked m‐terphenyl unit was prepared by Heck coupling between 1,4‐divinylbenzene and dibromides. The latter were synthesized through pyrylium salts. The polymer had optical band gap of 2.89 eV and emission maximum at 446 nm in THF solution and 434 nm in thin film. It showed a pure blue emission with no aggregates or excimers formed even in solid state because of the long and bulky pendant groups. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3842–3849, 2006     

Synthesis,electroluminescence, and photovoltaic cells of new vinylene‐copolymers with 4‐(anthracene‐10‐yl)‐2,6‐diphenylpyridine segments

Three new soluble vinylene‐copolymers F , C, and P that contain 4‐(anthracene‐10‐yl)‐2,6‐diphenylpyridine as common segment and fluorene, carbazole, or phenylene, respectively, as alternating segment were prepared by Heck coupling. The glass transition temperature was high for F and C (110 and 117°C), whereas was lower than 25°C for P . The polymers were stable up to ～ 300°C. They emitted blue–green light with maximum located at wavelength of 456–550 nm, which was of the order F < C < P . The photoluminescence quantum efficiency in THF solution was ～ 30% for F and P and only 5% for C . All three copolymers were used as active layers for polymer light emitting diodes (PLEDs) and organic photovoltaic cells. The double PLEDs with configuration of indium‐tin oxide (ITO)/poly(ethylenedioxythiophene (PEDOT) : poly(styrenesulfonate)(PSS)/Copolymer F , C , or P /TPBI(1,3,5‐tris(2‐N‐phenylbenzimidazolyl)benzene)/Ca/Al were fabricated. Copolymer P emitted green light with maximum brightness of 28 cd/m² and a current yield of 0.85 cd/A. Organic photovoltaics with the configuration of ITO/PEDOT : PSS/Copolymer and [6,6]‐phenyl‐C61‐butyric acid methyl ester blend (1 : 1) /Ca/Al were also fabricated. Copolymer P showed the highest power conversion efficiency of 0.034%. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

π-Conjugated poly(anthracene-alt-fluorene)s with X-shaped repeating units: New blue-light emitting polymers

A series of new π-conjugated poly(anthracene-alt-fluorene)s with X-shaped repeating units were synthesized. The polymers were easily soluble in common organic solvents and had good film-forming abilities. They showed high absolute PL quantum yields in the solid state. The electroluminescent devices based on the three X-shaped polymers with a configuration of ITO/PEDOT:PSS/polymer/LiF/Ca/Al emitted blue light with high brightness and low turn-on voltages.