Synthesis of electroluminescent copoly(aryl ether)s containing alternate 1,4‐distyrylbenzene derivatives and aromatic 1,3,4‐oxadiazole or 3,3″‐terphenyldicarbonitrile segments

New copoly(aryl ether)s ( P1 – P3 ) containing alternate 2,5‐dihexyloxy‐1,4‐di(m‐ethoxystyryl)benzene ( P1 , P2 ) or 2,5‐dihexyloxy‐1,4‐distyrylbenzene ( P3 ) chromophores and aromatic 1,3,4‐oxadiazole ( P1 ) or 3,3″‐terphenyldicarbonitrile ( P2 , P3 ) segments were prepared by Horner reaction ( P1 and P2 ) or nucleophilic displacement reaction ( P3 ). They are basically amorphous materials with 5% weight‐loss temperature above 410 °C. Their absorption, photoluminescence spectra, and quantum yields are dependent on the composition of the isolated fluorophores. The emissions are exclusively dominated by 1,4‐distyrylbenzene segments via excitation energy transfer from electron‐transporting 1,3,4‐oxadiazole ( P1 ) or 3,3″‐terphenyldicarbonitrile ( P2 , P3 ) chromophores. The HOMO and LUMO energy levels have been estimated from their cyclic voltammograms, and the observations confirm that oxidation and reduction start from the emitting 1,4‐distyrylbenzene and electron‐transporting segments, respectively, indicating that both carriers affinity can be enhanced simultaneously. Among the two‐layer PLED devices (ITO/PEDOT/ P1 – P3 /Al), P1 exhibits the best performance with a turn‐on field of 4 × 10⁵ V/cm and a maximum luminance of 225 cd/m². However, P2 emits green–yellow light (555 nm), owing to the excimer emission. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5009–5022, 2005     

Vinyl copolymers containing pendant 1,3,4-oxadiazole chromophores: Preparation and electrochemical and electroluminescent properties

Three vinyl copolymers (P1–P3) containing pendant aromatic 1,3,4-oxadiazole derivatives were prepared from their precursor poly(styrene-ran-4-vinylbenzyl chloride) (weight-average molecular weight = 11,400, polydispersity index = 1.18), which had been synthesized by controlled radical polymerization (reversible addition–fragmentation chain transfer). The copolymers were readily soluble in common organic solvents and were basically amorphous materials with 5% weight loss temperatures higher than 360°C. The photoluminescence spectroscopy results revealed that the architectures of P2 and P3 suppressed aggregate formation in the solid state. The LUMO levels of P2 (−3.10 eV) and P3 (−3.09 eV), estimated from cyclic voltammetry data, were much higher than that of P1 (−3.81 eV). The HOMO levels were in the order of P3 (−5.37 eV) > P2 (−5.77 eV) > P1 (−5.96 eV). However, both the HOMO and LUMO levels of P1–P3 were much lower than that of poly[2-methoxy-5-(2′-ethylhexoxy)-p-phenylenevinylene] (MEH-PPV) because of the electron-withdrawing characteristics of the pendant aromatic 1,3,4-oxadiazole groups. The luminance (5860 cd/m²) and current efficiency (1.45 cd/A) of an electroluminescence device [indium tin oxide/poly(3,4-ethylene dioxythiophene)/MEH-PPV/Al] were improved significantly to 16,261 cd/m² and 4.79 cd/A, respectively, through blending with P2 (50/50). This study suggests that copolymers P1–P3 are versatile materials for electron-transport/injection applications. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2259–2272, 2007     

Host copolymers containing pendant carbazole and oxadiazole groups: Synthesis,characterization and optoelectronic applications for efficient green phosphorescent OLEDs

Vinyl copolymers (PCOn), containing pendant carbazole and aromatic 1,3,4‐oxadiazole attached with dodecyloxy group, were prepared from their corresponding precursor poly(9‐vinyl carbazole‐co‐4‐vinylbenzyl chloride) (PCBn) by the Williamson condensation (n: mole% of 4‐vinylbenzyl chloride). These copolymers were used as host materials for green phosphorescent light‐emitting diodes after blending 4 wt % of Ir(ppy)₃. PL spectra of the PCOn films showed the formation of excimer or exciplex. The phosphorescent EL devices were fabricated with a configuration of ITO/PEDOT:PSS/host copolymers:Ir(ppy)₃/BCP/Ca/Al. The PL and EL spectra of the blends [PCOn:Ir(ppy)₃] revealed dominant green emission at 517 nm attributed to Ir(ppy)₃ due to efficient energy transfer from the host to Ir(ppy)₃. Efficient green phosphorescent OLEDs was obtained when employing copolymer PCO16 as the host and Ir(ppy)₃ as the guest. The maximal luminance efficiency and the maximal luminance of this device were 17.9 cd/A and 19,903 cd/m², respectively. After doped with Ir(ppy)₃, the morphology of the films, both controlled PCO20 and PCO20 with attached dodecyloxy groups, were investigated by tapping‐mode AFM and FE‐SEM. The film of PCO20 exhibited uniform, featureless image and showed much better device performance than PCO20, which have been attributed to good compatibility of PCO20 with Ir(ppy)₃. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5180–5193, 2008     

Synthesis and optoelectronic properties of luminescent poly(p‐phenylenevinylene) derivatives containing electron‐transporting 1,3,4‐oxadiazole groups

Three random copolymers ( P1–P3 ) comprising phenylenevinylene and electron‐transporting aromatic 1,3,4‐oxadiazole segments (11, 18, 28 mol %, respectively) were prepared by Gilch polymerization to investigate the influence of oxadiazole content on their photophysical, electrochemical, and electroluminescent properties. For comparative study, homopolymer poly[2‐methoxy‐5‐(2′‐ethylhexyloxy)‐1,4‐p‐phenylenevinylene] ( P0 ) was also prepared by the same process. The polymers ( P0–P3 ) are soluble in common organic solvents and thermally stable up to 410 °C under a nitrogen atmosphere. Their optical properties were investigated by absorption and photoluminescence spectroscopy. The optical results reveal that the aromatic 1,3,4‐oxadiazole chromophores in P1–P3 suppress the intermolecular interactions. The HOMO and LUMO levels of these polymers were estimated from their cyclic voltammograms. The HOMO levels of P0–P3 are very similar (?5.02 to ?5.03 eV), whereas their LUMO levels decrease readily with increasing oxadiazole content (?2.7, ?3.08, ?3.11, and ?3.19 eV, respectively). Therefore, the electron affinity of the poly(p‐phenylenevinylene) chain can be gradually enhanced by incorporating 1,3,4‐oxadiazole segments. Among the polymers, P1 (11 mol % 1,3,4‐oxadiazole) shows the best EL performance (maximal luminance: 3490 cd/m², maximal current efficiency: 0.1 cd/A). Further increase in oxadiazole content results in micro‐phase separation that leads to performance deterioration. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4377–4388, 2007     

Luminescent copoly(aryl ether)s consisting of alternate oxadiazole and 1,4‐distyrylbenzene derivatives: Synthesis and characterization

In an effort to decrease the electron‐injection barrier from the anode electrode, four copoly(aryl ether)s ( P1 – P4 ), consisting of alternating isolated electron‐transporting [2,5‐diphenyl‐1,3,4‐oxadiazole for P1 and P3 and 5,5′‐diphenyl‐2,2′‐p‐(2,5‐bishexyloxyphenylene)‐bis‐1,3,4‐oxadiazole for P2 and P4 ] and emitting chromophores (1,4‐distyryl‐2,5‐dihexyloxybenzene for P1 and P2 and 1,4‐distyryl‐2,5‐dihexylbenzene for P3 and P4 ), have been synthesized by the nucleophilic displacement reaction between bisfluoride and bisphenol monomers. They are basically amorphous materials with 5% weight‐loss temperature above 400 °C. The photoluminescence spectra and quantum yields of these copolymers are dependent on the compositions of the two isolated fluorophores. The highest occupied molecular orbital and lowest unoccupied molecular orbital energy levels of these copolymers have been estimated from their cyclic voltammograms. All the observations directly prove that the oxidation starts at the hole‐transporting segments. The electron affinity can be enhanced by the introduction of isolated electron‐transporting segments that lead to a charge‐injection balance. Single‐layer light‐emitting diodes (Al/ P1 – P4 /ITO glass) have been fabricated. P1 and P2 reveal blue electroluminescence, and P3 and P4 reveal purple‐blue electroluminescence. Moreover, the incorporation of bisoxadiazole units increases the electron affinity and reduces the turn‐on electric field better than one oxadiazole unit. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2765–2777, 2003     

Luminescent copolyethers containing isolated 1,4‐distyrylbenzene derivatives backbone and 7‐oxy‐4‐methylcoumarin side group: Synthesis and characterization

Four new copolyethers ( P1 – P4 ) consisting of two isolated emitting chromophores [2,5‐dihexyloxy‐1,4‐distyrylbenzene (HODSB) and 2,5‐dihexyloxy‐1,4‐di(4‐methylenestyryl)benzene (HOMDSB) for P1 and P2 , 2,5‐dihexyl‐1,4‐distyrylbenzene (HDSB) and HOMDSB for P3 and P4 ] in the backbone, in which P2 and P4 further contain electron‐transporting chromophores [7‐oxy‐4‐methylcoumarin (OMC)] in the side chain, were successfully prepared by the Heck coupling reaction. The photoluminescence spectra and quantum yields of the copolymers depended mainly on compositions of the isolated fluorophores. Their highest occupied molecular orbital and lowest unoccupied molecular orbital energy levels were estimated from their cyclic voltammograms. Electrochemical investigations proved that the oxidation started at hole‐transporting DSB segments, whereas reduction began at electron‐transporting OMC groups in P2 and P4 . The electron affinity of P2 and P4 was enhanced by introducing electron‐transporting OMC chromophores. Double‐layer light‐emitting diodes (ITO/PEDOT:PSS / polymer/Al) of P1 and P2 revealed green electroluminescence, and those of P3 and P4 emitted blue light. Moreover, incorporation of OMC side groups effectively reduced turn‐on electric field and enhanced luminance efficiency of the EL devices due to increased electron affinity. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 211–221, 2007     

Single layer light‐emitting diodes from copolymers comprised of mesogen‐jacketed polymer containing oxadiazole units and PVK

A series of copolymers PCt‐co‐Poly(N‐vinylcarbazole) were synthesized through common radical polymerization, in which P‐Ct as a kind of mesogen‐jacketed liquid crystalline polymer was introduced, and the effects of copolymers composing variation on the optical properties of the polymers were studied. The structures and properties of the copolymers were characterized and evaluated by thermogravimetric (TGA), UV, photoluminescence (PL), cyclic voltammetry (CV), and electroluminescence (EL) analyses. All the polymers enjoy high thermal stability. PL peaks in the film show blue‐shift compared with in solutions and fluorescent quantum efficiency decreased with the N‐vinylcarbazole (nvk) content increasing, which supported the efficient energy transfer from nvk units to the oxadiazole units. CV revealed that, with the incorporation of nvk to the copolymer, these copolymers had high‐lying HOMO energy levels ranging from ?5.94 to ?6.09 eV. Single‐layer light‐emitting diodes (LEDs) with the configuration of ITO/PEDOT/PCt‐nvk/Mg:Ag/Ag were fabricated, which emit a blue light around 450 and 490 nm with a maximum luminance of 703 cd/m². The device performance varies with the content of nvk and device configuration, with device configuration ( b ) and PCt‐nvk8 giving the best value of external quantum efficiency of 0.27%. We show here that by proper design copolymer structure and modification of device configuration can exhibit strong blue EL in higher external quantum efficiency. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 1843–1851, 2008     

Synthesis and characterization of bipolar copolymers containing oxadiazole and carbazole pendant groups and their application to electroluminescent devices

A series of random copolymers POC10{Poly(2,5‐bis[(5‐decyloxy‐phenyl)‐1,3,4‐oxadiazole]styrene)}‐co‐Poly(N‐vinylcarbazole) (PVK) with different nvk content were synthesized through common radical polymerization and were incorporated into light emitting diodes as emitting layers. The structures and properties of the copolymers were characterized and evaluated by GPC, TGA, DSC, UV, PL, CV, and EL analyses. All the polymers enjoy high thermal stability. Cyclic voltammetry revealed that, with the incorporation of N‐vinylcarbazole to the copolymer, these copolymers had high‐lying HOMO energy values, which facilitated hole injection. PL peaks in the film show blue‐shift compared with those in solutions and fluorescent quantum efficiency decreased with the nvk content increasing, which supported the efficient energy transfer from nvk units to the oxadiazole units. Single‐layer LEDs with the configuration of ITO/PEDOT/PC10‐nvk/Mg:Ag/Ag were fabricated, which emit a blue light around 440 and 490 nm with a maximum brightness of 675.3 cd/m² and luminous efficiency of 0.108 cd/A. Moreover, we fabricated electrophosphorescent device from bipolar transport copolymer PC10‐nvk4 as host material and an orange‐light‐emitting iridium phosphor IrMDPP as guest. The maximum luminous efficiency of 0.548 cd/A was obtained. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5452–5460, 2008     

Synthesis and opto‐electrical properties of dendron‐containing poly(2,3‐diphenyl‐1,4‐phenylenevinylene) derivatives

A new series of poly(2,3‐diphenyl‐1,4‐phenylenevinylene) derivatives containing dendritic side groups were synthesized. Different generations of dendrons were integrated on the pendant phenyl ring to investigate their effect on optical and electrical properties of final polymers. Homopolymers can not be obtained via the Gilch polymerization because of sterically bulky dendrons. By controlling the feed ratio of different monomers during polymerization, dendron‐containing copolymers with high molecular weights were obtained. The UV–vis absorption and photoluminescent spectra of the thin films are pretty close; however, quantum efficiency is significantly enhanced with increasing the generation of dendrons. The electrochemical analysis reveals that hole‐injection is also improved by increasing dendritic generation. Double‐layer light‐emitting devices with the configuration of ITO/PEDOT:PSS/polymer/Ca/Al were fabricated. High generation dendrons bring benefit of improved device performance. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3440–3450, 2007     

Synthesis and electro‐optical properties of light‐emitting polymers containing oxadiazole derivatives for light‐emitting diodes applications

Two PPV‐based bipolar polymers containing 1,3,4‐oxadiazole pendant groups were synthesized via the Gilch polymerization reaction for use in light‐emitting diodes (LEDs). The resulting polymers were characterized using ¹H and ¹³C NMR, elemental analysis, DSC, and TGA. These polymers were found to be soluble in common organic solvents and are easily spin‐coated onto glass substrates, producing high optical quality thin films without defects. The electro‐optical properties of ITO/PEDOT/polymer/Al devices based on these polymers were investigated using UV‐visible, PL, and EL spectroscopy. The turn‐on voltages of the OC₁Oxa‐PPV and OC₁₀Oxa‐PPV devices were found to be 8.0 V. The maximum brightness and luminescence efficiency of the OC₁Oxa‐PPV device were found to be 544 cd/m² at 19 V and 0.15 cd/A, respectively. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 1098–1110, 2008     

Synthesis and optical and electrochemical properties of copolymers containing 9,9‐dihexylfluorene and 9‐dimethylaminopropylcarbazole chromophores

Soluble and well‐defined 9,9‐dihexylfluorene and 9‐dimethylaminopropylcarbazole based copolymers PFCN and 5PFCN have been prepared by Suzuki coupling polymerization. For comparison, alternate copolymer of 9,9‐dihexylfluorene and 9‐hexylcarbazole (PFC) was also prepared with the same method. Furthermore, alternate copolymer of 9,9‐dihexylfluorene and 9‐dimethylethylammoniumpropylcarbazole (PFCNE) was prepared from PFCN by the ethylation of its dimethylaminopropyl groups with bromoethane. These copolymers were soluble in organic solvents and showed high glass‐transition temperatures (75–160 °C). The optimized architecture of PFCN from a simulation was a spiral, which was different from the linear structure of poly(9,9‐dihexylfluorene) (PFO). Thermogravimetric analysis showed that the residual weights of 5PFCN, PFCN, PFC, and PFCNE at 800 °C were all greater then 50%, whereas PFO showed complete thermal decomposition. Both the absorption and photoluminescence emission peaks of these copolymers showed blueshifts after the introduction of the carbazole units because of reduced conjugation. Moreover, the introduction of 9‐hexylcarbazole and 9‐dimethylamionpropylcarbazole moieties into copolymers PFC and PFCN, respectively, effectively prevented the excimer formation of PFO. According to cyclic voltammetry results, PFCNE containing quaternary amino pendant groups exhibited the most stable reduction–oxidation cycles. The turn‐on electric fields of their electroluminescence devices decreased with increasing carbazole content because of the more balanced carrier injection. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3882–3895, 2006     

Bipolar copoly(aryl ether) containing distyrylbenzene,triphenylamine, and 1,2,4‐triazole moieties: Synthesis and optoelectronic properties

A novel copoly(aryl ether) ( P1 ) consisting of alternate emitting segments (distyrylbenzene) and a bipolar moiety composed of directly linked electron‐transporting aromatic 1,2,4‐triazole and hole‐transporting triphenylamine was synthesized. The copoly(aryl ether) is readily soluble in common organic solvents and exhibit good thermal stability with thermal decomposition temperature above 450 °C. The emission and the photoluminescence quantum yield of the copolymer are dominated by the emitting segments (distyrylbenzene) with longer emissive wavelength. Electron affinity of P1 is evidently enhanced after introducing the isolated bipolar unit, as confirmed by the lowered lowest unoccupied molecular orbital level (–2.77 eV) relative to P0 without bipolar unit (–2.34 eV). This results in improved emission efficiency of its polymer light‐emitting diode (indium tin oxide/poly(3,4‐ethylene dioxythiophene):poly(styrene sulfonate)/ P1 /LiF/Ca/Al) due to more balanced charges injection and transport. Blending P1 with poly(9,9‐dihexylfluorene) ( PF ) further improves the efficiency of the device; the best performance was obtained for PF / P1 = 20/0.8 (w/w) with maximum luminance and maximum luminance efficiency being significantly enhanced to 3260 cd/m² and 1.08 cd/A, respectively, from 380 cd/m² and 0.009 cd/A of P1 ‐based device. These results demonstrate that the bipolar moiety can be used to enhance charges injection and transport of electroluminescent polymers. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Copolyfluorenes containing pendant bipolar carbazole and 1,2,4‐triazole groups: Synthesis,characterization, and optoelectronic applications

Three novel copolyfluorenes ( P1 ‐ P3 ) containing pendant bipolar groups (2.5–7.7 mol %), directly linked hole‐transporting carbazole and electron‐transporting aromatic 1,2,4‐triazole, were synthesized by the Suzuki coupling reaction and applied to enhance emission efficiency of polymer light‐emitting diodes based on conventional MEH‐PPV. The bipolar groups not only suppress undesirable green emission of polyfluorene under thermal annealing, but also promote electron‐ and hole‐affinity of the resulting copolyfluorenes. Blending the bipolar copolyfluorenes with MEH‐PPV results in significant enhancement of device performance [ITO/PEDOT:PSS/MEH‐PPV+ P1 , P2 or P3 /Ca(50 nm)/Al(100 nm)]. The maximum luminance and luminance efficiency were enhanced from 3230 cd/m² and 0.29 cd/A of MEH‐PPV‐only device to 15,690 cd/m² and 0.81 cd/A (blend device with MEH‐PPV/ P3 = 94/6 containing about 0.46 wt % of pendant bipolar residues), respectively. Our results demonstrate the efficacy of the bipolar copolyfluorenes in enhancing emission efficiency of MEH‐PPV. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Synthesis and optical properties of light‐emitting π‐conjugated polymers containing biphenyl and dithienosilole

Copolymers containing oligo(phenylene vinylene) (2.5), fluorene, and 4,4‐dihexyldithienosilole (DTS) units were synthesized and characterized. The π‐conjugated monomers were joined with the palladium(0)‐catalyzed Suzuki–Miyaura coupling reaction, thus forming either biphenyl– or phenyl–thiophene linkages. These polymers were photoluminescent, with the fluorescent quantum efficiency between 54 and 63% and with λ_max for fluorescence at ～448 nm in tetrahydrofuran. The presence of 5% DTS in the copolymers had little influence on the optical absorption and emission wavelengths. Double‐layer light‐emitting‐diode devices using these polymers as emissive layers had low turn‐on voltages (3.5–4 V) and moderate external quantum efficiencies (0.14–0.30%). The results show that DTS plays a positive role in improving the charge‐injection characteristics of poly(phenylene vinylene) materials. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2048–2058     

New blue electroluminescent n‐type polyfluorene copolymers with a 1,3,4‐oxadiazole unit in the main chain

Novel polyfluorene copolymers alternately having an 1,3,4‐oxadiazole unit in the main chain were prepared by both one‐step and two‐step methods for polyoxadiazole synthesis. They displayed highly efficient blue photoluminescence, the properties of which were affected by the extent of conjugation and the changes in the electron density by a side chain. An electrochemical analysis of the polymers using cyclic voltammetry suggested that they could be used as electron‐transport/hole‐blocking materials as well as blue emission materials for polymer light‐emitting diodes. A simple double‐layer device consisting of poly(N‐vinylcarbazole) as a hole‐transport layer and poly[(9,9′‐didodecylfluorene‐2,7‐diyl)‐alt‐((1,4‐bis(1,3,4‐oxadiazole)‐2,5‐di(2‐ethylhexyloxy)phenylene)‐5,5′‐diyl)] as an emission layer exhibited narrow blue electroluminescence with a maximum at 430 nm. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1058–1068, 2004     

Synthesis and optical and electrochemical properties of copolymers consisting of 9,9‐dihexylfluorene and aromatic triazole chromophores

Aromatic triazole chromophores were incorporated into polyfluorene in an attempt to increase electron affinity, to promote emission efficiency, and to diminish excimer formation. Poly(9,9‐dihexylfluorene) ( P1 ) and new copolymers with aromatic triazoles ( P2 – P4 ) were prepared by Suzuki coupling polymerization. In P2 , the aromatic triazole (3.8 mol %) was attached exclusively as terminal groups, whereas P3 and P4 were main‐chain copolymers containing 3.9 and 10.3 mol % aromatic triazole chromophores, respectively. The copolymers were soluble in common organic solvents and showed high decomposition temperatures (437–458 °C). The twisted structure between the triazole and fluorene increased the emission efficiency and effectively prevented excimer formation in P2 – P4 . After the introduction of the triazole units, the absorption spectra showed a blueshift (from 388 to 381 nm in chloroform) due to confined conjugation, but the photoluminescence spectra remained almost the same (417–418 nm); this was attributed to oligofluorene segments. No emission of triazole fluorophores was observed because of efficient energy transfer from the triazole to oligofluorene segments. However, incomplete energy transfer was observed in CH₃COOH. The optical stability upon thermal annealing was also improved by the incorporation of aromatic triazole segments. From cyclic voltammetry results, P2 – P4 , containing triazole groups, showed greater electron affinity (lowest unoccupied molecular orbital level = ?2.67 to ?2.71 eV) than P1 (?2.52 eV). Electroluminescence devices of P1 – P4 all exhibited excimer emissions (483–521 nm), which could also be diminished by the introduction of aromatic triazole chromophores. © 2006Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 136–146, 2007     

Bipolar copolymers comprised mesogen‐jacketed polymer containing oxadiazole units and PVK as host materials for electroluminescent devices

Nonconjugated bipolar transport polymers have been developed as host materials for electroluminescent devices by incorporating both electron‐transporting and hole‐transporting functionalities into copolymers. The random copolymer PCt‐nvk3‐7 containing mesogen‐jacketed segment of P‐Ct have been synthesized and characterized. The effect of mesogen‐jacketed segment content of these bipolar copolymers on device performance has been investigated. The results of polymer light‐emitting diodes (PLEDs) show that the jacketed content of copolymers has a significant effect on device performance: lowering charge transport and facilitating the hole‐electron recombination leads to much higher current efficiency. Applying these high triplet random copolymers as host, the maximum current efficiency of 0.70 cd/A and the maximum brightness of 1872.8 cd/m² was achieved for PCt‐nvk3‐7 with an orange‐emitting complex dopant. The results suggest that the bipolar copolymers PCt‐nvks can be good host polymers for electrophosphorescent devices. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7861–7867, 2008     

Synthesis and luminescence of yellow/orange‐emitting poly[tris(2,5‐dihexyloxy‐1,4‐phenylenevinylene)‐ alt‐(1,3‐phenylenevinylene)]s

Soluble yellow/orange‐emitting poly[tris(2,5‐dihexyloxy‐1,4‐phenylenevinylene)‐alt‐(1,3‐phenylenevinylene)] derivatives ( 6 ) were synthesized and characterized. These polymers contained oligo(p‐phenylene vinylene) chromophores of equal conjugation length, which were jointed via a common m‐phenylene unit. An optical comparison of 6 and its model compound ( 8 ) at room temperature and low temperatures revealed the similarity in their absorption and fluorescence band structures. The vibronic band structure of 6 was assigned with the aid of the spectroscopic data for 8 at the low temperatures. 6 was electroluminescent and had an emission maximum wavelength at approximately 565 nm. With the device indium tin oxide/PEDOT/ 6 /Ca configuration, the polymer exhibited an external quantum efficiency as high as 0.25%. Simple substitution on m‐phenylene of 6 raised the electroluminescence output by a factor of about 10. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5853–5862, 2004     

Green‐emitting poly[(1,3‐phenylenevinylene)‐alt‐ (1,4‐phenylenevinylene)]s: Effect of the substitution patterns on the optical properties

Green‐emitting substituted poly[(2‐hexyloxy‐5‐methyl‐1,3‐phenylenevinylene)‐alt‐(2,5‐dihexyloxy‐1,4‐phenylenevinylene)]s ( 6 ) were synthesized via the Wittig–Horner reaction. The polymers were yellow resins with molecular weights of 10,600. The ultraviolet–visible (UV–vis) absorption of 6 (λ_max = 332 or 415 nm) was about 30 nm redshifted from that of poly[(2‐hexyloxy‐5‐methyl‐1,3‐phenylenevinylene)‐alt‐(1,4‐phenylenevinylene)] ( 2 ) but was only 5 nm redshifted with respect to that of poly[(1,3‐phenylenevinylene)‐alt‐(2,5‐dihexyloxy‐1,4‐phenylenevinylene)] ( 1 ). A comparison of the optical properties of 1 , 2 , and 6 showed that substitution on m‐ or p‐phenylene could slightly affect their energy gap and luminescence efficiency, thereby fine‐tuning the optical properties of the poly[(m‐phenylene vinylene)‐alt‐(p‐phenylene vinylene)] materials. The vibronic structures were assigned with the aid of low‐temperature UV–vis and fluorescence spectroscopy. Light‐emitting‐diode devices with 6 produced a green electroluminescence output (emission λ_max ～ 533 nm) with an external quantum efficiency of 0.32%. Substitution at m‐phenylene appeared to be effective in perturbing the charge‐injection process in LED devices. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1820–1829, 2004     

Synthesis and electroluminescent properties of fluorene‐based copolymers containing electron‐withdrawing thiazole derivatives

We synthesized two fluorene‐based copolymers poly[(2,5‐bis(4‐hexylthiophen‐2‐yl)thiazolo[5,4‐day]thiazole‐5,5′‐diyl)‐alt‐(9,9′‐dioctylfluorene‐2,7‐diyl)] ( PF‐TTZT), and poly[(5,5′‐bis(4‐hexylthiophen‐2‐yl)‐2,2′‐bithiazole‐5,5′‐diyl)‐alt‐(9,9′‐dioctylfluorene‐2,7‐diyl)] (PF‐TBTT), which contain the electron‐withdrawing moieties, thiazolothiazole, and bithiazole, respectively. Through electrochemical studies, we found that these two polymers exhibit stable reversible oxidation and reduction behaviors. Moreover, the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy levels of PF‐TBTT are lower than those of PF‐TTZT, and the bandgap of PF‐TBTT is smaller than that of PF‐TTZT. Thus the bithiazole moiety in PF‐TBTT is more electron‐withdrawing than the thiazolothiazole moiety in PF‐TTZT. Light‐emitting devices with indium tin oxide (ITO)/poly(3,4‐ethylene dioxythiophene):poly(styrenesulfonate)(PEDOT)/polymer/bis(2‐methyl‐8‐quinolinato)‐4‐phenylphenolate aluminum (BAlq)/LiF/Al configurations were fabricated. The performance of the PF‐TBTT device was found to be almost three times better than that of the PF‐TTZT device, which is because electron injection from the cathode to PF‐TBTT is much easier than for PF‐TTZT. We also investigated the planarity and frontier orbitals of the electron donor‐acceptor (D‐A) moieties with computational calculations using ab initio Hartree–Fock with the split‐valence 6‐31G* basis set. These calculations show that TBTT has a more nonplanar structure than TTZT and that the bithiazole moiety is more electron‐withdrawing than thiazolothiazole. These calculations are in good agreement with the experimental results. © Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7148–7161, 2008