Poly(triphenylamine)s derived from oxidative coupling reaction: Substituent effects on the polymerization,electrochemical, and electro‐optical properties

A series of triphenylamine‐based polymers containing electron‐donating methoxy (? OCH₃) and electron‐withdrawing cyano or nitro (? CN or ? NO₂) substituents in the main chains have been designed and investigated. These conjugated polymers ( P1 – P3 ) could be readily prepared by oxidative coupling polymerization from monomers ( M1 – M3 ) using FeCl₃ as an oxidant. The P2 and P3 exhibited moderate high T_g values (203–205 °C) and thermal stability. These polymers in NMP solution showed UV–vis absorption around 288–404 nm and photoluminescence peaks around 435–492 nm. P1 – P3 showed reversible oxidation redox couples at E_onset = 0.67, 0.99, and 1.00 V in solution of 0.1 M tetrabutylammonium perchlorate (TBAP)/acetonitrile (CH₃CN), respectively. M3 and P3 exhibited reversible reduction redox couples at E_onset = ?1.04 and ?1.03 V. These polymers also revealed electrochromic characteristic changing color at different potential. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 285–294, 2009     

Synthesis and characterization of novel π‐conjugated polymers with phosphole ring derivatives

Novel π‐conjugated polymers ( 8 – 10 ) were prepared by the palladium‐catalyzed Sonogashira coupling reaction of three kinds of phosphole‐ring‐containing monomers with 2,5‐dihexyloxyl‐1,4‐diethynylbenzene. The obtained polymers ( 8 – 10 ) were regioregulated with the 2,5‐substituted phosphole ring in the polymer main chain and characterized with ¹H, ¹³C, and ³¹P NMR and FTIR. Polymers 8 – 10 were found to have an extended π‐conjugated system according to the results of UV–vis absorption spectra. In the fluorescence emission spectra of 8 – 10 , moderate emission peaks were observed in the visible blue‐to‐green region. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2867–2875, 2007     

New poly(arylene ether)s with pendant phosphonic acid groups

Soluble brominated poly(arylene ether)s containing mono‐ or dibromotetraphenylphenylene ether and octafluorobiphenylene units were synthesized. The polymers were high molecular weight (weight‐average molecular weight = 115,100–191,300; number‐average molecular weight = 32,300–34,000) and had high glass‐transition temperatures (>279 °C) and decomposition temperatures (>472 °C). The brominated polymers were phosphonated with diethylphosphite by a palladium‐catalyzed reaction. Quantitative phosphonation was possible when 50 mol % of a catalyst based on bromine was used. The diethylphosphonated polymers were dealkylated by a reaction with bromotrimethylsilane in carbon tetrachloride followed by hydrolysis with hydrochloric acid. The polymers with pendant phosphonic acid groups were soluble in polar solvents such as dimethyl sulfoxide and gave flexible and tough films via casting from solution. The polymers were hygroscopic and swelled in water. They did not decompose at temperatures of up to 260 °C under a nitrogen atmosphere. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3770–3779, 2001     

Soluble narrow‐band‐gap copolymers containing novel cyclopentadithiophene units for organic photovoltaic cell applications

Five novel conjugated copolymers ( P1 – P5 ) containing coplanar cyclopentadithiophene (CPDT) units (incorporated with arylcyanovinyl and keto groups in different molar ratios) were synthesized and developed for the applications of polymer solar cells (PSCs). Polymers P1 – P5 covered broad absorption ranges from UV to near infrared (400–900 nm) with narrow optical band gaps of 1.38–1.70 eV, which are compatible with the maximum solar photon reflux. Partially reversible p‐ and n‐doping processes of P1 – P5 in electrochemical experiments were observed, and the proper molecular design for highest occupied molecular orbital (HOMO)/lowest unoccupied molecular orbital (LUMO) levels of P1 – P5 induced the highest photovoltaic open‐circuit voltage in the PSC devices, compared with those previously reported CPDT‐based narrow‐band‐gap polymers. Powder X‐ray diffraction (XRD) analyses suggested that these copolymers formed self‐assembled π‐π stacking and pseudobilayered structures. Under 100 mW/cm² of AM 1.5 white‐light illumination, bulk heterojunction PSC devices containing an active layer of electron donor polymers P1 – P5 mixed with electron acceptor [6,6]‐phenyl C₆₁ butyric acid methyl ester (PCBM) in the weight ratio of 1:4 were investigated. The PSC device containing P1 gave the best preliminary result with an open‐circuit voltage of 0.84 V, a short‐circuit current of 2.36 mA/cm², and a fill factor of 0.38, offering an overall power conversion efficiency (PCE) of 0.77% as well as a maximal quantum efficiency of 23% from the external quantum efficiency (EQE) measurements. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2073–2092, 2009     

Synthesis and properties of blue light‐emitting,silicon‐containing,regio‐ and stereoregular conjugated polymers

This article concerns the hydrosilylation polyaddition of 1,4‐bis(dimethylsilyl)benzene ( 1 ) with 4,4′‐diethynylbiphenyl, 2,7‐diethynylfluorene ( 2b ), and 2,6‐diethynylnaphthalene with RhI(PPh₃)₃ catalyst. Trans‐rich polymers with weight‐average molecular weights (M_w's) ranging from 19,000 to 25,000 were obtained by polyaddition in o‐Cl₂C₆H₄ at 150–180 °C, whereas cis‐rich polymers with M_w's from 4300 to 34,000 were obtained in toluene at 0 °C–r.t. These polymers emitted blue light in 4–81% quantum yields. The cis polymers isomerized into trans polymers upon UV irradiation, whereas the trans polymers did not. The device having a layer of polymer trans‐ 3b obtained from 1 and 2b demonstrated electroluminescence without any dopant. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2774–2783, 2004     

Poly(pyridinium salt)s with stilbene or distyrylbenzene chromophores

A new series of poly(pyridinium salt)s that contained side stilbenyl groups or p‐distirylbenzene segments in the main chain were synthesized from the reactions of bis(pyrylium salts) with diamines. They were characterized by viscometry, Fourier transform infrared spectroscopy, NMR, X‐ray scattering, differential scanning calorimetry, thermomechanical analysis, ultraviolet–visible analysis, and luminescence spectroscopy. The polymers were amorphous and soluble in polar aprotic solvents such as dimethylacetamide, dimethylformamide, and dimethyl sulfoxide. The glass‐transition temperatures were in the range of 59–123 °C. These polymers had initial decomposition temperatures of 240–295 °C and afforded anaerobic char yields of 29–53% at 800 °C. Both the absorption and photoluminescence (PL) spectra of the polymers were studied, and the PL quantum yields in solution were determined. The polymers showed violet‐blue fluorescence in solution with PL maxima at 408–416 nm and violet‐green fluorescence in thin film with PL maxima at 454–523 nm. The structure of the diamine utilized for the preparation of the polymers did not influence their PL maxima. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2454–2462, 2001     

Synthesis,photophysics, theoretical modeling,and electroluminescence of novel 2,7‐carbazole‐based conjugated polymers with sterically hindered structures

2,7‐dibromo‐N‐hexylcarbazole is successfully synthesized in three steps with an overall 37% yield. Novel 2,7‐carbazole‐based sterically hindered conjugated polymers are further synthesized. In the backbone structure of polymer P1 , alkylated bithiophene moiety is β‐substituted with dodecyl chains on both thiophene rings, adopting the tail‐to‐tail configuration. While for polymers P2 and P3 , partially planarized thieno[3,2‐b]thiophene moiety ( P2 ) and β‐pentyl substituted thieno[3,2‐b]thiophene ( P3 ) are incorporated. All polymers demonstrate efficient blue‐to‐green light emission, good thermal stability (T_d ≥ 379 °C), and high glass transition temperatures (T_g = 118 °C). The optical and electronic properties of the resulted polymers are tuned by the incorporated alkyl chains. For instance, the incorporation of β‐pentyl group in thieno[3,2‐b]thiophene moiety endows P3 with blue‐shifted photophysical spectra, reduced fluorescence quantum yield and larger band gap in comparison with P2 . The steric effect of incorporated alkyl chains is further illustrated by geometry optimization of three model oligomers (analogues to the repetition units of P1–P3 ) using density functional theory. Sterically hindered polymers P1 and P2 exhibit high charge transport ability and moderate electroluminescent properties in primarily tested single‐layer light‐emitting diodes (configuration: ITO/PEDOT:PSS/Polymer/Ca/Ag). © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7725–7738, 2008     

Synthesis of polymers containing 1,2,4‐oxadiazole as an electron‐acceptor moiety in their main chain and their solar cell applications

To explore the aptitude of 1,2,4‐oxadiazole‐based electron‐acceptor unit in polymer solar cell applications, we prepared four new polymers (P1–P4) containing 1,2,4‐oxadiazole moiety in their main chain and applied them to solar cell applications. Thermal, optical, and electrochemical properties of the polymers were studied using thermogravimetric, absorption, and cyclic voltammetry analysis, respectively. All four polymers showed high thermal stability (5% degradation temperature over 335 °C), and the optical band gaps were calculated to be 2.20, 1.72, 1.37, and 1.74 eV, respectively, from the onset wavelength of the film‐state absorption band. The energy levels of the polymers were found to be suitable for bulk heterojunction (BHJ) solar cell applications. The BHJ solar cells were prepared by using the synthesized polymers as a donor and PC₇₁BM as an electron acceptor with the configuration of ITO/PEDOT:PSS/polymer:PC₇₁BM (1:3 wt %)/LiF/Al. One of the polymers was found to show the maximum power conversion efficiency of 1.33% with a Jsc of 4.95 mA/cm², a V_oc of 0.68 V, and a FF of 40%, measured using AM 1.5 G solar simulator at 100 mW/cm₂ light illumination. © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Synthesis and photovoltaic properties of two‐dimensional D‐A copolymers with conjugated side chains

Four novel two‐dimensional (2D) donor–acceptor (D‐A) type copolymers with different conjugated side chains, P1 , P2 , P3 , and P4 (see Fig. 1 ), are designed and synthesized for the application as donor materials in polymer solar cells (PSCs). To the best of our knowledge, there were few reports to systematically study such 2D polymers with D‐A type main chains in this area. The optical energy band gaps are about 2.0 eV for P1 – P3 and 1.67 eV for P4 . PSC devices using P1 – P4 as donor and [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester as acceptor in a weight ratio of 1:3 were fabricated and characterized to investigate the photovoltaic properties of the polymers. Under AM 1.5 G, 100 mA/cm² illumination, a high open‐circuit voltage (V_oc) of 0.9 V was recorded for P3 ‐based device due to its low HOMO level, and moderate fill factor was obtained with the best value of 58.6% for P4 ‐based device, which may mainly be the result of the high hole mobility of the polymers (up to 1.82 × 10^?3 cm²/V s). © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Synthesis and structural characterization of novel,fluorinated poly(phthalazinone ether)s containing perfluorophenylene moieties

The synthesis and structural characterization of a series of novel, fluorinated poly(phthalazinone ether)s containing perfluorophenylene moieties are described. The monomers, 4‐(4′‐hydroxyaryl)phthalazin‐1(2H)‐ones ( 2a – 2d ), were conveniently and efficiently synthesized from phenols and phthalic anhydride in two steps via 2‐(4′‐hydroxybenzoyl)benzoic acids, which were first obtained by the Friedel–Crafts reaction in good yields and with high stereoselectivity and were then converted into 2a – 2d by fusion with hydrazine. All the polymers were prepared by nucleophilic aromatic substitution (S_NAr) polycondensation between the compounds perfluorobiphenyl and 4‐(4′‐hydroxyaryl)phthalazin‐1(2H)‐ones ( 2a ‐ 2d ). The resulting fluorinated polymers were readily soluble in common organic solvents (e.g., CHCl₃, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide, N‐methylpyrrolidone, etc.) at room temperature. Their weight‐average molecular weights and the polydispersities ranged from (7.96–18.25) × 10³ to 1.31–2.71, respectively. Their glass‐transition temperatures varied from 213 to 263 °C. They were all stable up to 390 °C both in air and in argon. The 5% weight‐loss temperatures of these polymers in air and argon ranged from 393–487 to 437–509 °C, respectively. Wide‐angle X‐ray diffraction studies indicated they were all amorphous and could be attributed to the presence of kink nonplanar moiety, phenyl phthalazinone along the polymer backbone. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 925–932, 2004     

Synthesis of novel dithienothiophene‐ and 2,7‐carbazole‐based conjugated polymers and H‐bonded effects on electrochromic and photovoltaic properties

Three kinds of dithienothiophene/carbazole‐based conjugated polymers ( P1–P3 ), which bear acid‐protected and benzoic acid pendants in P2 and P3 , respectively, were synthesized via Suzuki coupling reaction. Interestingly, P1 – P3 exhibited reversible electrochromism during the oxidation processes of cyclic voltammogram studies, and P3 (with H‐bonds) revealed the best electrochromic property with the most noticeable color change. According to powder X‐ray diffraction (XRD) analysis, these polymers exhibited obvious diffraction features indicating bilayered packings between polymer backbones and π‐π stacking between layers in the solid state. Compared with the XRD data of P2 (without H‐bands), H‐bonds of P3 induced a higher crystallinity in the small‐angle region (corresponding to a higher ordered bilayered packings between polymer backbones), but with a similar crystallinity in the wide angle region indicating a comparable π‐π stacking distance between layers. Moreover, based on the preliminary photovoltaic properties of PSC devices ( P1 – P3 blended individually with PCBM acceptor in the weight ratio of 1:1), P3 (with H‐bonds) possessed the highest power conversion efficiency of 0.61% (with J_sc = 2.26 mA/cm², FF = 29.8%, and V_oc = 0.9 V). In contrast to P2 (without H‐bands), the thermal stability, crystallinity, and electrochromic along with photovoltaic properties of P3 were generally enhanced due to its H‐bonded effects. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Synthesis and optical and electrochemical properties of novel copolymers containing alternating 2,3‐divinylquinoxaline and hole‐transporting units

For the enhancement of charge affinity, electron‐affinitive 2,3‐divinylquinoxaline and a series of hole‐transporting chromophores (iminodibenzyl, phenothiazine, dihexyloxybenzene, and didodecyloxydistyrylbenzene) were incorporated alternately into the polymeric main chain. The resulting copolymers ( P1 – P4 ) were basically amorphous materials and were thermally stable below 300 °C. The electronic structures, photoluminescence, and electrochemical properties of these copolymers were mainly determined by the electron‐donating chromophores in the backbone. They showed significant positive solvatochromism in formic acid. An electrochemical study revealed that they exhibited lower band gaps (<2.3 eV) due to alternating donor and acceptor conjugated units (push–pull structure). Single‐layer light‐emitting diodes of aluminum, P1 – P4 , and indium tin oxide glass were fabricated, and preliminary electroluminescence spectra showed that P1 , P3 , and P4 were orange‐emitting materials. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 4570–4580, 2002     

High‐temperature elastomers from silarylene‐siloxane‐diacetylene linear polymers

The syntheses and characterization of linear silarylene‐siloxane‐diacetylene polymers 3a–c and their thermal conversion to crosslinked elastomeric materials 4a–c are discussed. Inclusion of the diacetylene unit required synthesis of an appropriate monomeric species. 1,4‐Bis(dimethylaminodimethylsilyl)butadiyne [(CH₃)₂N? Si(CH₃)₂? C?C? C?C? (CH₃)₂Si? N(CH₃)₂] 2 was prepared from 1,4‐dilithio‐1,3‐butadiyne and 2 equiv of dimethylaminodimethylchlorosilane. The linear polymers were prepared via polycondensation of 2 with a series of disilanol prepolymers. The low molecular weight silarylene‐siloxane prepolymers 1a–c (terminated by hydroxyl groups) were synthesized via solution condensation of an excess amount of 1,4‐bis(hydroxydimethylsilyl)benzene with bis(dimethylamino)dimethylsilane. The linear polymers were characterized by ¹H and ¹³C NMR, Fourier transform infrared spectroscopy, gel permeation chromatography, thermogravimetric analysis (TGA), and DSC. The elastomers exhibited long‐term oxidative stability up to 330 °C in air as determined by TGA. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 40: 88–94, 2002     

Triphenylamine‐based polyimides with trimethyl substituents for gas separation membrane and electrochromic applications

Two series of polyimides I – II with methyl‐substituted triphenylamine units were prepared from the diamines, 4,4′‐diamino‐2″,4″,6″‐trimethyltriphenylamine (Me₃TPA‐diamine; 1 ) and 4,4′‐diamino‐4″‐methyltriphenylamine (MeTPA‐diamine; 2 ), and two commercially available tetracarboxylic dianhydrides via a conventional two‐step chemical imidization. All the polymers were readily soluble in many polar solvents and showed useful levels of thermal stability associated with high glass transition temperatures (266–340 °C) and high char yields (higher than 49% at 800 °C in nitrogen). The polymer films showed reversible electrochemistry/electrochromism accompanied by a color change from neutral pale yellow to green oxidized form with good coloration efficiency, switching time, and stability. The CO₂ permeability coefficients (P_CO2) and permeability selectivity (P_CO2/P_CH4) for these polyimide membranes were in the range of 34.1–229.2 barrer and 21.3–28.9, respectively. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

π‐conjugated polymers having diaza[12]annulene rings and aminopenta‐2,4‐dienylidene groups generated by the ring opening of pyridinium rings

Reactions of N‐(2,4‐dinitrophenyl)pyridinium chloride with 2,5‐dimethyl‐1,4‐phenylenediamine in 1:2, 1:1.5, 1:1, and 2:1 molar ratios caused the ring opening of the pyridinium ring and thereby yielded polymers ( P1 – P4 ) consisting of 5‐(2,5‐dimethyl‐1,4‐phenylene)penta‐2,4‐dienylideneammonium chloride (unit A) and N‐2,5‐dimethyl‐1,4‐phenylene diaza[12]annulenium dichloride (unit B). The ¹H NMR spectra suggested that the composition ratios of unit A to unit B in P1 – P4 were 0.98:0.02, 0.94:0.06, 0.81:0.19, and 0.79:0.21, respectively. P1 – P4 showed an absorption maximum (λ_max) at a longer wavelength than the monomers because of the expansion of the π‐conjugation system. Films of P3 and P4 showed λ_max at a considerably longer wavelength than those in solution, and this was attributable to the ordered structures of the polymers in the solid state. Powder X‐ray diffraction analysis supported the ordered structures of P3 and P4 . Pellets molded from P3 and P4 exhibited a metallic luster, whereas those from P1 and P2 did not show such a luster. Cyclic voltammetry measurements indicated that P1 – P4 were electrochemically active in films. The thermal stability of the polymers depended on the composition ratios of unit A to unit B. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1507–1514, 2007     

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     

Polymers with alternating anthracene and phenylene building blocks linked by ethynylene and/or vinylene units: Studying structure‐properties‐relationships

Four conjugated polymers ( P1 – P4 ) consisting of alternating anthracene‐9,10‐diyl and 1,4‐phenylene building blocks connected via ethynylene as well as vinylene ( P1 and P2 ), ethynylene‐only ( P3 ), and vinylene‐only ( P4 ) moieties, respectively, were synthesized and studied. The phenylene units in all four polymers bear 2‐ethylhexyloxy side‐chains to promote good solubility. The three polymers with vinylene units ( P1 , P2 , and P4 ) were prepared using the Horner–Wadsworth–Emmons reaction. For the synthesis of the arylene‐ethynylene polymer P3, the palladium‐catalyzed Sonogashira cross‐coupling reaction was used. The polymers were characterized by NMR, Fourier transform infrared spectroscopy, and Raman spectroscopy. Photophysical, absorption and photoluminescence, and electrochemical properties were studied. Spectroscopic ellipsometry measurements were performed to gain more insight on the optical properties. In addition, the transport properties were investigated using admittance spectroscopy. The bulk hole mobility and its dependence on the electric field were evaluated for P1 and P2 . © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 129–143     

Synthesis,photophysics, and electroluminescent performance of stable blue‐light‐emitting copoly(9,9‐diarylfluorene)s

A series of fluorene derivatives containing nonsymmetric and bulky aromatic groups at C‐9 position were synthesized and used for the preparation of blue‐light‐emitting copolyfluorenes ( P1 – P4 ) by the Suzuki coupling polycondensation. The copolymers were characterized by molecular weight determination, elemental analysis, differential scanning calorimeter, thermogravimetric analysis, absorption and emission spectroscopy, cyclic voltammetry, and differential pulse voltammetry. Their decomposition temperatures and glass transition temperatures are 423–441 °C and >120 °C, respectively. In film state, the copolyfluorenes exhibit blue photoluminescence at 425–450 nm, which remains almost unchanged after annealing at 200 °C in air for 60 min. Polymer light‐emitting diodes [ITO/PEDOT:PSS/ P1 – P4 /Ca(50 nm)/Al(100 nm)] show stable blue‐light emission under device operation with the CIE co‐ordinates being between (0.16, 0.07) and (0.17, 0.09). The light‐emitting diodes devices from P1 and P3 containing electron‐deficient oxadiazole units display enhanced performance, with the maximum brightness and maximum current efficiency being (4510 cd/m² and 2.40 cd/A) and (2930 cd/m², 1.19 cd/A), respectively. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2821–2834, 2009     

Thermally stable,light‐emitting,triphenylamine‐containing poly(amine hydrazide)s and poly(amine‐1,3,4‐oxadiazole)s bearing pendent carbazolyl groups

A series of new organosoluble poly(amine hydrazide)s were synthesized via the Yamazaki phosphorylation reaction and were solution‐cast into transparent films. Differential scanning calorimetry indicated that the hydrazide polymers 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 exhibited glass‐transition temperatures in the range of 276–297 °C, 10% weight loss temperatures in excess of 520 °C, and char yields at 800 °C in nitrogen higher than 67%. The hole‐transporting and electrochromic properties were examined with electrochemical and spectroelectrochemical methods. Cyclic voltammograms of these polymers prepared by the casting of polymer solutions onto an indium tin oxide coated glass substrate exhibited two reversible oxidative redox couples at 1.10–1.19 and 1.35–1.60 V versus Ag/AgCl in an acetonitrile solution, respectively. The poly(amine hydrazide)s revealed excellent stability of the electrochromic characteristics, changing color from the original pale yellow to green and then to blue. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 48–58, 2007     

Glycoconjugated polymer. I. Synthesis and characterization of amphiphilic polystyrenes with glucose,maltose, and maltohexaose as hydrophilic segments

Glucosyl styrene ( 1a ), maltosyl styrene ( 1b ), and maltohexaosyl styrene ( 1c ) were prepared by the glycosylation of 4‐vinylbenzyl alcohol with the corresponding glycosyl trichloroacetimidates with boron trifluoride diethyl ether complex. The copolymerizations of 1a – 1c with styrene were carried out with 2,2′‐azobis(2‐methylpropionitrile) as an initiator in dry N,N‐dimethylformamide at 60 °C, and this was followed by deacetylation to produce amphiphilic polystyrenes with glucose ( 3a ), maltose ( 3b ), and maltohexaose ( 3c ) as hydrophilic segments. 3 showed various solubility characteristics that were dependent on the content of glucose residues, especially within a range of 20–50 wt %. The solubility characteristics of 3 , related to the copolymer composition, indicated that the hydrophilic property was remarkably improved with an increased number of glucose units, that is, in the order 3a < 3b ? 3c . The results described in this article provide useful information for the design of glycoconjugated architectures with desired amphiphilic properties. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 4061–4067, 2001