Synthesis,photoluminescence, and electrochromism of novel aromatic poly(amine‐1,3,4‐oxadiazole)s bearing anthrylamine chromophores

Two novel poly(amine‐hydrazide)s were prepared from the polycondensation reactions of the dicarboxylic acid, 9‐[N,N‐di(4‐carboxyphenyl)amino]anthracene ( 1 ), with terephthalic dihydrazide ( TPH ) and isophthalic dihydrazide ( IPH ) via the Yamazaki phosphorylation reaction, respectively. The poly(amine‐hydrazide)s were readily soluble in many common organic solvents and could be solution cast into transparent films. Differential scanning calorimetry (DSC) indicated that these hydrazide polymers had glass‐transition temperatures (T_g) in the range of 182–230 °C and could be thermally cyclodehydrated into the corresponding oxadiazole polymers in the range of 300–400 °C. The resulting poly(amine‐1,3,4‐oxadiazole)s had useful levels of thermal stability associated with high T_g (263–318 °C), 10% weight‐loss temperatures in excess of 500 °C, and char yield at 800 °C in nitrogen higher than 55%. These organo‐soluble anthrylamine‐based poly(amine‐hydrazide)s and poly (amine‐1,3,4‐oxadiazole)s exhibited maximum UV‐vis absorption at 346–349 and 379–388 nm in N‐methyl‐2‐pyrrolidone (NMP) solution, respectively. Their photoluminescence spectra in NMP solution showed maximum bands around 490–497 nm in the green region. The poly(amine‐hydrazide) I ‐ IPH showed a green photoluminescence at 490 nm with PL quantum yield of 29.9% and 17.0% in NMP solution and film state, respectively. The anthrylamine‐based poly(amine‐1,3,4‐oxadiazole)s revealed a electrochromic characteristics with changing color from the pale yellow neutral form to the red reduced form when scanning potentials negatively from 0.00 to ?2.20 V. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1584–1594, 2009     

Soluble,redox‐active,and blue‐emitting poly(amide‐hydrazide)s and poly(amide‐1,3,4‐oxadiazole)s containing pyrenylamine units

Two new aromatic poly(amide‐hydrazide)s (PAHs)‐bearing electroactive pyrenylamine units in the backbone were prepared from the phosphorylation polycondensation reactions of N,N‐di(4‐carboxyphenyl)‐1‐aminopyrene ( 1 ) with p‐aminobenzoyl hydrazide (p‐ABH) and m‐aminobenzoyl hydrazide (m‐ABH), respectively. The PAHs could be further cyclodehydrated into the corresponding poly(amide‐1,3,4‐oxadiazole)s in the range of 300–400 °C in the solid film state. All the hydrazide and oxadiazole polymers were soluble in many polar organic solvents and could afford flexible and strong films via solution casting. The poly(amide‐1,3,4‐oxdiazole)s had high glass‐transition temperatures (294–309 °C) and high thermal stability (10% weight‐loss temperature in excess of 520 °C). The dilute solutions of all the hydrazide and oxadiazole polymers showed strong fluorescence with emission maxima around 457–459 nm in the blue region. Copolymers obtained from the polycondensation of equimolar mixture of diacid 1 and 4,4′‐oxydibenzoic acid with p‐ABH or m‐ABH exhibited a significantly increased fluorescence quantum efficiency in comparison with the homopolymers. Cyclic voltammetry results indicated that all the hydrazide and oxadiazole polymers exhibited an ambipolar (n‐ and p‐doping processes) and electrochromic behavior. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011.     

Novel thermally stable poly(amine hydrazide)s and poly(amine‐1,3,4‐oxadiazole)s for luminescent and electrochromic materials

We describe the preparation, characterization, and luminescence of four novel electrochromic aromatic poly(amine hydrazide)s containing main‐chain triphenylamine units with or without a para‐substituted N,N‐diphenylamino group on the pendent phenyl ring. These polymers were prepared from either 4,4′‐dicarboxy‐4″‐N,N‐diphenylaminotriphenylamine or 4,4′‐dicarboxytriphenylamine and the respective aromatic dihydrazide monomers via a direct phosphorylation polycondensation reaction. All the poly(amine hydrazide)s were amorphous and readily soluble in many common organic solvents and could be solution‐cast into transparent and flexible films with good mechanical properties. These poly(amine hydrazide)s exhibited strong ultraviolet–visible absorption bands at 346–348 nm in N‐methyl‐2‐pyrrolidone (NMP) solutions. Their photoluminescence spectra in NMP solutions or as cast films showed maximum bands around 508–544 and 448–487 nm in the green and blue region for the two series of polymers. The hole‐transporting and electrochromic properties were examined by electrochemical and spectroelectrochemical methods. All obtained poly(amine hydrazide)s and poly(amine‐1,3,4‐oxadiazole)s exhibited two reversible oxidation redox couples at 0.8 and 1.24 V vs. Ag/AgCl in acetonitrile solution and revealed excellent stability of electrochromic characteristics, changing color from original pale yellow to green and then to blue at electrode potentials of 0.87 and 1.24 V, respectively. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3245–3256, 2005     

Aromatic poly(1,3,4‐oxadiazole)s and poly(amide‐1,3,4‐oxadiazole)s containing ether sulfone linkages

Polyhydrazides and poly(amide‐hydrazide)s were prepared from two ether‐sulfone‐dicarboxylic acids, 4,4′‐[sulfonylbis(1,4‐phenylene)dioxy]dibenzoic acid and 4,4′‐[sulfonylbis(2,6‐dimethyl‐1,4‐phenylene)dioxy]dibenzoic acid, or their diacyl chlorides with terephthalic dihydrazide, isophthalic dihydrazide, and p‐aminobenzhydrazide via a phosphorylation reaction or a low‐temperature solution polycondensation. All the hydrazide polymers were found to be amorphous according to X‐ray diffraction analysis. They were readily soluble in polar organic solvents such as N‐methyl‐2‐pyrrolidone and N,N‐dimethylacetamide and could afford colorless, flexible, and tough films with good mechanical strengths via solvent casting. These hydrazide polymers exhibited glass‐transition temperatures of 149–207 °C and could be thermally cyclodehydrated into the corresponding oxadiazole polymers in the solid state at elevated temperatures. Although the oxadiazole polymers showed a significantly decreased solubility with respect to their hydrazide prepolymers, some oxadiazole polymers were still organosoluble. The thermally converted oxadiazole polymers had glass‐transition temperatures of 217–255 °C and softening temperatures of 215–268 °C and did not show significant weight loss before 400 °C in nitrogen or air. For a comparative study, related sulfonyl polymers without the ether groups were also synthesized from 4,4′‐sulfonyldibenzoic acid and the hydrazide monomers by the same synthetic routes. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2271–2286, 2001     

Synthesis and photoluminescent and electrochromic properties of aromatic poly(amine amide)s bearing pendent N‐carbazolylphenyl moieties

A series of novel poly(amine amide)s ( IIa – IIl ) with pendent N‐carbazolylphenyl units having inherent viscosities of 0.25–1.06 dL/g were prepared via direct phosphorylation polycondensation from various dicarboxylic acids and a carbazole‐based aromatic diamine. Except for poly(amine amide) IIc , derived from trans‐1,4‐cyclohexanedicarboxylic acid, all the other amorphous poly(amine amide)s were readily soluble in many polar solvents, such as N,N‐dimethylacetamide and N‐methyl‐2‐pyrrolidone (NMP), and could be cast into transparent and flexible films. The aromatic poly (amine amide)s had useful levels of thermal stability associated with relatively high glass‐transition temperatures (268–331 °C), 10% weight loss temperatures in excess of 540 °C, and char yields at 800 °C in nitrogen higher than 60%. These polymers exhibited maximum ultraviolet–visible absorption at 293–361 nm in NMP solutions. Their photoluminescence in NMP solutions exhibited fluorescence emission maxima around 362 and 448–499 nm for aromatic–aliphatic poly(amine amide)s IIa – IIc and aromatic poly (amine amide)s IId – IIl , respectively. The fluorescence quantum yield in NMP solutions ranged from 0.34% for IIj to 4.44% for IIa . The hole‐transporting and electrochromic properties were examined with electrochemical and spectroelectrochemical methods. Cyclic voltammograms of the poly(amine amide) films cast onto an indium tin oxide coated glass substrate exhibited reversible oxidation at 0.81 V and irreversible oxidation redox couples at 1.20 V versus Ag/AgCl in acetonitrile solutions, and they revealed excellent stability of the electrochromic characteristics, with a color change from yellow to green at applied potentials ranging from 0.00 to 1.05 V. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4108–4121, 2006     

Synthesis and properties of noncoplanar rigid‐rod aromatic polyhydrazides and poly(1,3,4‐oxadiazole)s containing phenyl or naphthyl substituents

Two new phenyl‐ and naphthyl‐substituted rigid‐rod aromatic dicarboxylic acid monomers, 2,2′‐diphenylbiphenyl‐4,4′‐dicarboxylic acid ( 4 ) and 2,2′‐di(1‐naphthyl)biphenyl‐4,4′‐dicarboxylic acid ( 5 ), were synthesized by the Suzuki coupling reaction of 2,2′‐diiodobiphenyl‐4,4′‐dicarboxylic acid dimethyl ester with benzeneboronic acid and naphthaleneboronic acid, respectively, followed by alkaline hydrolysis of the ester groups. Four new polyhydrazides were prepared from the dicarboxylic acids 4 and 5 with terephthalic dihydrazide (TPH) and isophthalic dihydrazide (IPH), respectively, via the Yamazaki phosphorylation reaction. These polyhydrazides were amorphous and readily soluble in many organic solvents. Differential scanning calorimetry (DSC) indicated that these hydrazide polymers had glass transition temperatures in the range of 187–234 °C and could be thermally cyclodehydrated into the corresponding oxadiazole polymers in the range of 300–400 °C. The resulting poly(1,3,4‐oxadiazole)s exhibited T_g's in the range of 252–283 °C, 10% weight‐loss temperature in excess of 470 °C, and char yield at 800 °C in nitrogen higher than 54%. These organo‐soluble polyhydrazides and poly(1,3,4‐oxadiazole)s exhibited UV–Vis absorption maximum at 262–296 and 264–342 nm in NMP solution, and their photoluminescence spectra showed maximum bands around 414–445 and 404–453 nm, respectively, with quantum yield up to 38%. The electron‐transporting properties were examined by electrochemical methods. Cyclic voltammograms of the poly(1,3,4‐oxadiazole) films cast onto an indium‐tin oxide (ITO)‐coated glass substrate exhibited reversible reduction redox with E_onset at ?1.37 to ?1.57 V versus Ag/AgCl in dry N,N‐dimethylformamide solution. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6466–6483, 2006     

Synthesis and properties of fluorine‐containing poly(aryl ether oxadiazole)s

Fluorine‐containing poly(aryl ether 1,3,4‐ozadiazole)s were synthesized by the nucleophilic aromatic substitution reaction of 2,5‐bis(2,3,4,5,6‐pentafluorophenyl)‐1,3,4‐oxadiazole and various bisphenols in the presence of potassium carbonate. The polymerizations were carried out at 30 °C in 1‐methyl‐2‐pyrrolidinone to avoid the gelation caused by a crosslinking reaction at para and ortho carbons to the 1,3,4‐oxidiazole ring. The obtained polymers were all para‐connected linear structures. The obtained fluorine‐containing poly(aryl ether 1,3,4‐ozadiazole)s showed excellent solubility and afforded tough, transparent films by the solution‐casting method. They also exhibited a high glass transition temperature depending on the molecular structure, and the glass transition temperature could be controlled by the bisphenols in the range of 157–257 °C. They showed good thermal stability and excellent hydrophobicity due to the incorporation of the 2,3,5,6‐tetrafluoro‐1,4‐phenylene moiety. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2855–2866, 2007     

Synthesis and properties of novel aromatic polyhydrazides and poly(amide–hydrazide)s based on the bis(ether benzoic acid)s from hydroquinone and substituted hydroquinones

4,4′‐(1,4‐Phenylenedioxy)dibenzoic acid as well as the 2‐methyl‐, 2‐tert‐butyl‐, or 2‐phenyl‐substituted derivatives of this dicarboxylic acid were synthesized in two main steps from p‐fluorobenzonitrile and hydroquinone or its methyl‐, tert‐butyl‐, or phenyl‐substituted derivatives. Polyhydrazides and poly(amide–hydrazide)s were prepared from these bis(ether benzoic acid)s or their diacyl chlorides with terephthalic dihydrazide, isophthalic dihydrazide, or p‐aminobenzoyl hydrazide by means of the phosphorylation reaction or low‐temperature solution polycondensation. Most of the hydrazide polymers and copolymers are amorphous and readily soluble in various polar solvents such as N‐methyl‐2‐pyrrolidone (NMP) and dimethyl sulfoxide. They could be solution‐cast into transparent, flexible, and tough films. These polyhydrazides and poly(amide–hydrazide)s had T_gs in the range of 167–237°C and could be thermally cyclodehydrated into the corresponding poly(1,3,4‐oxadiazole)s and poly(amide–1,3,4‐oxadiazole)s approximately in the region of 250–350°C, as evidenced by the DSC thermograms. All the tert‐butyl‐substituted oxadiazole polymers and those derived from isophthalic dihydrazide were organic soluble. The thermally converted oxadiazole polymers exhibited T_gs in the range of 208–243°C and did not show significant weight loss before 450°C either in nitrogen or in air. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1169–1181, 1999     

Synthesis and properties of poly(imide‐hydrazide)s and poly(amide‐imide‐hydrazide)s from N‐[p‐(or m‐)carboxyphenyl]trimellitimide and aromatic dihydrazides or p‐aminobenzhydrazide via the phosphorylation reaction

A series of new poly(imide‐hydrazide)s and poly(amide‐imide‐hydrazide)s were obtained by the direct polycondensation of N‐[p‐(or m‐)carboxyphenyl]trimellitimide (p‐ or m‐CPTMI) with terephthalic dihydrazide (TPH), isophthalic dihydrazide (IPH), and p‐aminobenzhydrazide (p‐ABH) by means of diphenyl phosphite and pyridine in the N‐methyl‐2‐pyrrolidone (NMP) solutions containing dissolved CaCl₂. The resulting hydrazide‐containing polymers exhibited inherent viscosities in the 0.15–0.96 dL/g range. Except for that derived from p‐CPTMI with TPH or p‐ABH, the other hydrazide copolymers were readily soluble in polar solvents such as NMP and dimethyl sulfoxide (DMSO). As evidenced by X‐ray diffraction patterns, the hydrazide copolymer obtained from TPH showed a moderate level of crystallinity, whereas the others were amorphous in nature. Most of the amorphous hydrazide copolymers formed flexible and tough films by solvent casting. The amorphous hydrazide copolymers had glass‐transition temperatures (T_g) between 187 and 233 °C. All hydrazide copolymers could be thermally converted into the corresponding oxadiazole copolymers approximately in the region of 250–400 °C, as evidenced by the DSC thermograms. The oxadiazole copolymers showed a significantly decreased solubility when compared to their respective hydrazide precursors. They exhibited T_g's of 264–302 °C and did not show dramatic weight loss before 400 °C in air or nitrogen. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 1599–1608, 2000     

Synthesis of a new class of triphenylamine‐containing poly(ether‐imide)s for electrochromic applications

A novel triphenylamine (TPA)‐containing bis(ether anhydride) monomer, namely 4,4′‐bis(3,4‐dicarboxyphenoxy)triphenylamine dianhydride, was synthesized and reacted with various aromatic diamines leading to a series of new poly(ether‐imide)s (PEI). Most of these PEIs were soluble in organic solvents and could be easily solution cast into flexible and strong films. The polymer films exhibited good thermal stability with glass‐transition temperatures in the range 211–299 °C. The polymer films exhibited reversible electrochemical processes and stable color changes (from transparent to navy blue) with high coloration efficiency and contrast ratio upon electro‐oxidation. During the electrochemical oxidation process, a crosslinked polymer structure was developed due to the coupling reaction between the TPA radical cation moieties in the polymer chains. These polymers can be used to fabricate electrochromic devices with high coloration efficiency, high redox stability, and fast response time. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 825–838     

Red,green, and blue electrochromism in ambipolar poly(amine–amide–imide)s based on electroactive tetraphenyl‐p‐phenylenediamine units

A series of novel poly(amine–amide–imide)s (PAAIs) based on tetraphenyl‐p‐phenylenediamine (TPPA) units showing anodically/cathodically electrochromic characteristic with three primary colors [red, green, and blue (RGB)] were prepared from the direct polycondensation of the TPPA‐based diamine monomer with various aromatic bis(trimellitimide)s. These multicolored electrochromic polymers were readily soluble in polar organic solvents and showed excellent thermal stability associated with high glass‐transition temperatures (288–314 °C) and high‐char yield (higher than 60% at 800 °C in nitrogen). The PAAI films revealed electrochemical oxidation and reduction accompanied with high contrast of optical transmittance color changes from the pale yellow neutral state to the green/blue oxidized state and red reduced state, respectively. The electrochromic films had high‐coloration efficiency (CE = 178 and 242 cm²/C at the first and the second stages, respectively), low‐switching time, and good redox stability, which still retained a high electroactivity after long‐term redox cycles. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Near‐infrared electrochromic poly(aryl ether)s based on isolated electroactive tetraphenyl‐p‐phenylenediamine moieties

A series of near‐infrared (NIR) electrochromic aromatic poly(aryl ether)s containing N,N,N′,N′‐tetraphenyl‐p‐phenylenediamine (TPPA) moieties in the backbone were prepared from the high‐temperature polycondensation reactions of a biphenol monomer, 2,5‐bis(diphenylamino)hydroquinone, with difluoro compounds. The obtained polymers were readily soluble in many organic solvents and showed useful levels of thermal stability associated with high glass‐transition temperatures (182–205 °C) and high char yields (higher than 40% at 800 °C in nitrogen). The polymer films showed reversible electrochemical oxidation with high contrast ratio both in the visible range and NIR region, and also exhibited high coloration efficiency (CE), low switching time, and stability for electrochromic operation. The polyether TPPA‐a thin film revealed good CE in visible (CE = 217 cm²/C) and NIR (CE = 192 cm²/C) region with reversible electroactive stability (over 500 times within 5% loss relative to its initial injected charge). © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5378–5385, 2009     

One‐pot synthesis of linear and branched poly(amide aspartimide)s with good solubility in organic solvents

Linear and branched poly(amide aspartimide)s were prepared through the reaction of 4,4′‐diaminodiphenylmethane with 4‐maleimidobenzoic acid and 5‐maleimidoisophthalic acid, respectively. The synthesis was performed through a one‐pot operation by means of the Michael addition reaction between amine and maleimide groups and the dehydration condensation reaction between amine and carboxylic acid groups. The obtained polymers exhibited fairly good solubility in aprotic polar solvents at room temperature and in pyridine, tetrahydrofuran, acetone, and chloroform upon heating. High glass‐transition temperatures (≥225 °C) and thermal stability above 360 °C were found for the polymers. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1923–1929, 2005     

Novel family of triphenylamine‐containing,hole‐transporting,amorphous, aromatic polyamides with stable electrochromic properties

We report the preparation and characterization of a series of novel electrochromic, aromatic poly(amine amide)s with pendent triphenylamine units. The synthesis proceeded via direct phosphorylation polycondensation between a novel diamine, N,N‐bis(4‐aminophenyl)‐N′,N′‐diphenyl‐1,4‐phenylenediamine, and various aromatic dicarboxylic acids. All the poly(amine amide)s were amorphous and readily soluble in many common organic solvents and could be solution‐cast into transparent, tough, and flexible films with good mechanical properties. They exhibited good thermal stability and 10% weight‐loss temperatures above 540 °C. Their glass‐transition temperatures were 263–290 °C. These polymers in N‐methyl‐2‐pyrrolidinone solutions exhibited strong ultraviolet–visible absorption peaks at 307–358 nm and photoluminescence peaks around 532–590 nm in the green region. The hole‐transporting and electrochromic properties were studied with electrochemical and spectroelectrochemical methods. Cyclic voltammograms of poly(amine amide) films prepared by the casting of polymer solutions onto an indium tin oxide coated glass substrate exhibited two reversible oxidation redox couples at 0.65 and 1.03 V versus Ag/AgCl in an acetonitrile solution. All the poly(amine amide)s showed excellent stability with respect to their electrochromic characteristics; the color of the films changed from pale yellow to green and then blue at 0.85 and 1.25 V, respectively. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2085–2098, 2005     

Synthesis and properties of wholly aromatic polymers bearing cardo fluorene moieties

Three series of aromatic polyamides, polyesters, and poly(1,3,4‐oxadiazole)s containing bulky fluorene structures were prepared from 9,9‐bis(4‐carboxyphenyl) fluorene. All of the polymers were readily soluble in many organic solvents and showed useful thermal stability associated with high glass‐transition temperatures in the range of 220–366 °C. These wholly aromatic polymer films were colorless, with high optical transparency, and exhibited UV‐vis absorption bands at 266–348 nm and photoluminescence maximum bands at 368–457 nm within the purple to green region in N,N‐dimethylacetamide (DMAc) solutions. The poly(amine‐amide) Ic exhibited excellent electrochromic contrast and coloration efficiency, changing color from the colorless neutral form to green and then to the dark blue oxidized forms with good stability of electrochromic characteristics. Almost all of these wholly aromatic polymer films were colorless and showed high optical transparency. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4352–4363, 2007     

Thermal and optical properties of some phosphorus‐containing poly(1,3,4‐oxadiazole‐ester‐imide)s

A series of phosphorus‐containing poly(1,3,4‐oxadiazole‐ester‐imide)s was prepared by polycondensation reaction of an aromatic dianhydride, namely 1,4‐[2‐(6‐oxido‐6H‐dibenz<c,e><1,2>oxaphosphorin‐6‐yl)]‐naphthalene‐bis(trimellitate)dianhydride, with different aromatic diamines containing 1,3,4‐oxadiazole ring. A solution imidization procedure was used to convert quantitatively the poly(amic acid) intermediates to the corresponding polyimides. The chemical structures of the monomers and polymers were confirmed by Fourier transform infrared, ¹H NMR and ³¹P NMR spectroscopy. The polymers were easily soluble in polar solvents such as N‐methyl‐2‐pyrrolidone (NMP), N,N‐dimethylformamide and tetrahydrofuran. They exhibited good thermal properties having the decomposition temperature above 380°C and the glass transition temperature in the range of 201–232°C. Due to the presence of phosphorus the polymers gave high char yield in termogravimetric analysis, hence good flame retardant properties. Optical properties were analyzed in solution by using UV–vis and photoluminescence spectroscopy. Solutions of the polymers in NMP exhibited photoluminescence in the blue region. Copyright © 2010 John Wiley & Sons, Ltd.     

New P‐type of poly(4‐methoxy‐triphenylamine)s derived by coupling reactions: Synthesis,electrochromic behaviors,and hole mobility

Methoxy‐substituted poly(triphenylamine)s, poly‐4‐methoxytriphenylamine ( PMOTPA ), and poly‐N,N‐bis(4‐methoxyphenyl)‐N′,N′‐diphenyl‐p‐phenylenediamine ( PMOPD ), were synthesized from the nickel‐catalyzed Yamamoto and oxidative coupling reaction with FeCl₃. All synthesized polymers could be well characterized by ¹H and ¹³C NMR spectroscopy. These polymers possess good solubility in common organic solvent, thermal stability with relatively high glass‐transition temperatures (T_gs) in the range of 152–273 °C, 10% weight‐loss temperature in excess of 480 °C, and char yield at 800 °C higher than 79% under a nitrogen atmosphere. They were amorphous and showed bluish green light (430–487 nm) fluorescence with quantum efficiency up to 45–62% in NMP solution. The hole‐transporting and electrochromic properties are examined by electrochemical and spectroelectrochemical methods. All polymers exhibited reversible oxidation redox peaks and E_onset around 0.44–0.69 V versus Ag/AgCl and electrochromic characteristics with a color change under various applied potentials. The series of PMOTPA and PMOPD also showed p‐type characteristics, and the estimated hole mobility of O ‐ PMOTPA and Y ‐ PMOPD were up to 1.5 × 10^?4 and 5.6 × 10^?5 cm² V^?1 s^?1, respectively. The FET results indicate that the molecular weight, annealing temperature, and polymer structure could crucially affect the charge transporting ability. This study suggests that triphenylamine‐containing conjugated polymer is a multifunctional material for various optoelectronic device applications. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4037–4050, 2009     

Synthesis and properties of new soluble triphenylamine‐based aromatic poly(amine amide)s derived from N,N′‐bis(4‐carboxyphenyl)‐N,N′‐diphenyl‐1,4‐phenylenediamine

A new triphenylamine‐containing aromatic dicarboxylic acid, N,N′‐bis(4‐carboxyphenyl)‐N,N′‐diphenyl‐1,4‐phenylenediamine, was synthesized by the condensation of N,N′‐diphenyl‐1,4‐phenylenediamine with 4‐fluorobenzonitrile, followed by the alkaline hydrolysis of the intermediate dinitrile compound. A series of novel triphenylamine‐based aromatic poly(amine amide)s with inherent viscosities of 0.50–1.02 dL/g were prepared from the diacid and various aromatic diamines by direct phosphorylation polycondensation. All the poly(amine amide)s were amorphous in nature, as evidenced by X‐ray diffractograms. Most of the poly(amine amide)s were quite soluble in a variety of organic solvents and could be solution‐cast into transparent, tough, and flexible films with good mechanical properties. They had useful levels of thermal stability associated with glass‐transition temperatures up to 280 °C, 10% weight‐loss temperatures in excess of 575 °C, and char yields at 800 °C in nitrogen higher than 60%. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 94–105, 2003     

Thermotropic liquid‐crystalline poly(oxadiazole)s with poly(methylene) spacers: Preparation and extraordinary odd–even effect

A novel synthetic procedure for the preparation of poly(oxadiazole)s was developed with nucleophilic substitution of α,ω-alkanediols with oxadiazole-activated bisfluoride. Seven poly(oxadiazole)s were successfully prepared by the solution polymerization of 2,5-bis(4-fluorophenyl)-1,3,4-oxadiazole and various α,ω-alkanediols [HO (CH₂)_n OH, n = 5–10 or 12] in diphenyl sulfone at temperature greater than 230 °C with K₂CO₃ as a catalyst. The reduced viscosities of the poly(oxadiazole)s were 0.14–0.51 dL/g, and the decomposition temperatures were greater than 350 °C and decreased from 436 to 379 °C with increasing spacer length (n). Corresponding model compounds, consisting of two terminal mesogenic 2,5-bisphenyl-1,3,4-oxadiazole units and central poly(methylene) spacers, were also prepared for comparison. Both the polymers and model compounds exhibited an extraordinary odd–even effect: odd ones showed higher transition temperatures (melting and clearing temperatures). With differential scanning calorimetry, polarized optical microscopy (POM), and X-ray diffraction, we found that the nematic mesophase was the only texture in the melts except for the polymers with longer methylene units (n = 9), in which smectic mesophases were observed. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 40: 293–301, 2002     

Synthesis,optical properties,and electroluminescence of conjugated poly(p‐phenylenevinylene) derivatives containing 1,3,4‐oxadiazole and pyridine rings in the main chain

Three new poly(p‐phenylenevinylene) derivatives—PO, POD, and POP—with oxadiazole and pyridine rings along the main chain were synthesized via Heck coupling. The polymers were amorphous and dissolved readily in common organic solvents. They showed relatively low glass‐transition temperatures (up to 42 °C) and satisfactory thermal stability. Solutions of the polymers emitted blue‐greenish light with photoluminescence (PL) emission maxima around 460 nm and PL quantum yields of 0.28–0.49. Thin films of the polymers displayed PL emission maxima at 461–521 nm, and their tendency to form aggregates was significantly influenced by the chemical structure. Light‐emitting diodes with polymers PO and POP, with an indium tin oxide/poly(ethylenedioxythiophene) (PEDOT)/polymer/Ca configuration, emitted yellow and green light, respectively, and this could be attributed to excimer emission. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3212–3223, 2004