Poly(4-nitrophenyl)quinoxalines

Via the reaction of 4,4-bis(4-nitrophenylglyoxalyl)diphenyl ether with different bis(o-phenylenediamine)s, new poly(4-nitrophenyl)quinoxalines were synthesized, which are of interest as precursors for polymers containing protogenic groups. Some properties of the obtained polymers were studied. It was shown that the solubility of poly(4-nitrophenyl)quinoxalines in organic solvents and their viscosity characteristics are comparable with the parameters of polyphenylquinoxalines that do not bear nitro groups. A study of the thermal properties of the polymers showed that the introduction of nitro groups into polyphenylquinoxalines is accompanied by some increase in the glass transition temperature and a decrease in the onset temperature of runaway thermal degradation.     

Novel aromatic polymers from benzaldehyde and triphenylamine derivatives: Synthesis,electrochromic, and photochemical properties

A series of novel triphenylamine‐based polymers were synthesized from benzaldehyde and triphenylamine derivatives. All the polymers having high molecular weight are readily soluble in many organic solvents and could be solution‐cast into amorphous films. They had glass transition temperatures (T_gs) in the range of 193–217 °C, and 10% weight loss temperatures in excess of 475 °C. Cyclic voltammograms of all polymers showed reversible oxidation redox peaks and E_onset around 0.42–0.90 V, indicating that the polymers are electrochemically active and stable. In addition, all these polymers revealed photochemical characteristics in conformity with their electrochromic characteristics. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2118–2131, 2009     

Branched polyphenylquinoxalines containing naphthoxazine-5,8-disulfonic acid groups

Branched carboxylated polyphenylquinoxalines are prepared via the interaction of tris(α-diketone), 4,4′-bis(phenylglyoxalyl)benzyl, with an equimolar amount of 3,4-diaminobenzoic acid and subsequent interaction of the reaction product with an equimolar amount of bis(o-phenylenediamines). Polymeranalogous transformations of these polymers with 1-amino-8-naphthol-3,6-disulfonic acid sodium salt monohydrate in Eaton’s reagent yield earlier undescribed branched polyphenylquinoxalines containing side naphthoxazine-5,8-disulfonic acid groups.     

Molecular engineering tuning optoelectronic properties of thieno[3,2-<Emphasis Type="Italic">b</Emphasis>]thiophenes-based electrochromic polymers

Thieno[3,2-b]thiophene (TT) monomers end-capped with 3,4-ethylenedioxythiophene (EDOT) moieties are electropolymerized to form π-conjugated polymers with distinct electrochromic (EC) properties. Steric and electronic factors (electron donor and acceptor substituents) in the side groups of the TT core, as well as the structure of the polymer backbone strongly affect the electrochemical and optical properties of the polymers and their electrochromic characteristics. The studied polymers show low oxidation potentials, tunable from–0.78 to +0.30 V (vs. Fc/Fc⁺) and the band gaps from 1.46 to 1.92 eV and demonstrate wide variety of color palettes in polymer films in different states, finely tunable by structural variations in the polymer backbone and the side chains. EC materials of different colors in their doped/dedoped states have been developed (violet, deep blue, light blue, green, brown, purple-red, pinkish-red, orange-red, light gray, cyan and colorless transparent). High optical contrast (up to 79%), short response time (0.57–0.80 s), good cycling stability (up to 91% at 2000 cycles) and high coloration efficiency (up to 234.6 cm² C^–1) have been demonstrated and the influence of different factors on the above parameters of EC polymers have been discussed.     

Soluble alkyl substituted poly(3,4‐propylenedioxyselenophene)s: A new platform for optoelectronic materials

Optical and electrochemical properties of regiosymmetric and soluble alkylenedioxyselenophene‐based electrochromic polymers, namely poly(3,3‐dibutyl‐3,4‐dihydro‐2H‐selenopheno[3,4‐b][1,4]dioxephine) (PProDOS‐C₄), poly(3,3‐dihexyl‐3,4‐dihydro‐2H‐selenopheno[3,4‐b][1,4]dioxephine) (PProDOS‐C₆), and poly(3,3‐didecyl‐3,4‐dihydro‐2H‐selenopheno[3,4‐b][1,4]dioxephine) (PProDOS‐C₁₀), are highlighted. It is noted that these unique polymers have low bandgaps (1.57–1.65 eV), and they are exceptionally stable under ambient atmospheric conditions. Polymer films retained 82–97% of their electroactivity after 5000 cycles. The percent transmittance of PProDOS‐C_n (n = 4, 6, 10) films found to be between 55 and 59%. Furthermore, these novel soluble PProDOS‐C_n polymers showed electrochromic behavior: a color change form pure blue to highly transparent state in a low switching time (1.0 s) during oxidation with high coloration efficiencies (328–864 cm² C^?1) when compared to their thiophene analogues. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Synthesis and photophysical properties of polyphenylquinoxalines with thiophene and benzothiophene units in side chains

New bis(α-diketones) with thiophene and benzothiophene moieties were synthesized. A series of new polyphenylquinoxalines containing these moieties in side chains was prepared via polycondensation of these diketones with different aromatic tetramines. The polymers are soluble in a variety of organic solvents, and their solutions form transparent films having a tensile strength of σ = 80–100 MPa and an elongation at break of ? = 5–12%. The polymers exhibit fluorescence in solution in trifluoroacetic acid and in films with a maximum at 430–570 and 460–480 nm. The 10% mass loss temperature in air ranges within 440–490°C.     

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     

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     

New carbazole-containing polyphenylquinoxalines: Synthesis,photophysical, and electroluminescent properties

New carbazole-containing polyphenylquinoxalines combining the electron-transport behavior of quinoxaline with hole-transport and electroluminescent properties of carbazole have been synthesized. The polymers show solubility in organic solvents. Their glass transition temperatures range from 315 to 370°C, and temperatures corresponding to 10% weight loss vary from 510 to 560°C (in air). It has been demonstrated that these polymers exhibit electroluminescent behavior in the 450–750 nm spectral region and offer promise as emitting and electron-hole transport materials for polymeric light-emitting diodes.     

Polyphenylquinoxalines with high glass transition temperatures via highly fused aromatic tetraamines

A series of polyphenylquinoxalines has been synthesized by the reaction of p,p′-oxydibenzil with aromatic tetraamines containing varying numbers of fused rings. It was found that the glass transition temperatures of the resultant polymers increased as the the number of adjacent fused rings in the polymers was increased. This provided the basis for achieving glass transition temperatures for the polymers in excess of 400°C, substantially higher than the state-of-the art polyphenylquinoxalines. All of the polymers displayed both the good thermal stability and the solubility in m-cresol characteristic of the polyphenylquinoxaline family of polymers.     

Enhancing electrochromic contrast and redox stability of nanostructure polypyrrole film doped by heparin as polyanion in different solvents

Heparin‐doped polypyrrole (PPy‐Hep) and ‐doped polypyrrole (PPy‐ClO₄) films are synthesized onto FTO‐coated glass electrode in a potentiostatic electrochemical process with the aim of producing uniform, transparent, and adherent coating. The resultant polymers are characterized via cyclic voltammetry, scanning electron microscopy (SEM), and UV–vis absorption spectroscopy. SEM study indicates that the PPy‐Hep film to be composed of a continuous interlinked network of quasi spherical grains (50–80 nm in dimensions). The electrochromic properties of PPy‐Hep and PPy‐ClO₄ polymer films are compared to spectroelectrochemistry and switching studies. The effect of different solvents (water, propylene carbonate, and acetonitrile) on the electrochromic features of electropolymerized polymers has been investigated, and we find a very significant solvent effect. PPy‐Hep film exhibits switching time of 1 s and the maximum transmittance contrast (ΔT%) is 48% at 800 nm in water. In addition, presence of Hep causes drastic enhancement of electro‐optical stability of PPy. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 3365–3371     

Synthesis and electrochromism of novel organosoluble polyarylates bearing triphenylamine moieties

A series of novel aromatic polyarylates with triphenylamine units in the main chain and as the pendent group were prepared from the dicarboxylic acid monomer, N,N‐bis(4‐carboxyphenyl)‐N′, N′‐diphenyl‐1,4‐phenylenediamine (1), and various bisphenols. These polyarylates were amorphous and readily soluble in common organic solvents. They had excellent levels of thermal stability associated with moderately high T_g values (182–263 °C). These polymers exhibited strong UV–vis absorption bands at 357–360 nm in toluene solution and the photoluminescence spectra showed maximum bands around 493–503 nm in the green region. The hole‐transporting and electrochromic properties were examined by electrochemical and spectroelectrochemical methods. Cyclic voltammograms of the polyarylates exhibited two reversible oxidation redox couples in acetonitrile solution at E_onset 0.77–0.79 V and 1.12–1.14 V, respectively. The typical polymer 3b film revealed good stability of electrochromic characteristics, with color change from colorless to green and blue at applied potentials ranging from 0.00 to 1.24 V. These anodically polymeric electrochromic materials not only showed excellent reversible electrochromic stability with good green coloration efficiency (CE = 159 cm²/C) and blue coloration efficiency (CE = 154 cm²/C) but also exhibited high contrast of optical transmittance change (ΔT%), 54% in 895 nm for green color and up to 84% in 595 nm for blue color. After over 100 cyclic switches, the polymer films still exhibited excellent stability of electrochromic characteristics. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2004–2014, 2007     

Synthesis and evaluation of photoluminescent and electrochemical properties of new aromatic polyamides and polyimides with a kink 1,2‐phenylenediamine moiety

A series of novel triphenylamine‐containing aromatic polyamides and polyimides having a crank and twisted noncoplanar structures were synthesized in inherent viscosities of 0.14–0.64 dL/g and 0.11–0.67 dL/g, respectively. These polymers had useful levels of thermal stability associated with relatively high glass‐transition temperatures (174–311 °C). They exhibited strong UV–Vis absorption bands at around 300 nm in NMP solutions. The PL spectra of these polymers in NMP solutions (1 × 10^?5 M) showed maximum peaks around 396–479 nm. The hole‐transporting and electrochromic properties were examined by electrochemical and spectroelectrochemical methods. Cyclic voltammetry (CV) of the polymer films cast onto an indium‐tin oxide (ITO)‐coated glass substrate exhibited two reversible oxidation redox couples at potentials of 0.70–1.01 V and 1.10–1.46 V, respectively, vs. Ag/AgCl in acetonitrile solution. The polymer films revealed electrochromic characteristics, with a color change from neutral pale yellowish to green and then to a blue oxidized form at applied potentials ranging from 0.00 to 1.75 V. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2587–2603, 2006     

SYNTHESIS AND PROPERTIES OF POLYPHENYLQUINOXALINES CONTAINING CHLORO-ATOM

Several polyphenylquinoxalines (PPQ's) containing chloro-atom in the side chain have been syn-thesized and characterized by IR, TGA, ITGA and DTA. High quality, flekible, glass-cast films andvarnished wires have been obtained. The T_g's values and thermal stabilities of these polymers wereguater than those without any chloro-atom substitutent.     

Membranotropic properties of fullerene-containing amphiphilic (co)polymers of <Emphasis Type="Italic">N</Emphasis>-vinylpyrrolidone

The effect of fullerene-containing amphiphilic (co)polymers of N-vinylpyrrolidone (C₆₀/PVP) differed in composition and topology of the polymer chains on the membrane structure of phosphatidylcholine liposomes was studied. Using the method of fluorescent probes it was found that the C₆₀/PVP structures under study are localized in the phosphatidylcholine membrane in the region of glycerol fragments and fatty acid chains of phospholipids. The C₆₀/PVP copolymers form complexes with 2,7-dibromoproflavin and pyrene probes. The effective equilibrium constants of the probe–C₆₀/PVP complexes in aqueous solutions and in the liposome membrane were determined. It is most likely that the fullerene-containing (co)polymers of N-vinylpyrrolidone form complexes not only with fluorescent probes but also with phospholipids of the liposome membrane, which reduces the stability of the probe–C₆₀/PVP complex.     

High Tg,ambipolar, and near‐infrared electrochromic anthraquinone‐based aramids with intervalence charge‐transfer behavior

Two novel series of ambipolar and near‐infrared electrochromic aromatic polyamides with electroactive anthraquinone group were synthesized from new aromatic diamines, 2‐(bis(4‐aminophenyl)amino)anthracene‐9,10‐dione and 2‐(4‐(bis(4‐aminophenyl)amino)phenoxy)anthracene‐9,10‐dione, respectively, via low‐temperature solution polycondensation reaction. These polymers were readily soluble in many polar solvents and showed useful levels of thermal stability associated with high glass‐transition temperatures (T_g) (285–360 °C). Electrochemical studies of these electrochromic polyamides revealed ambipolar behavior with reversible redox couples and high contrast ratio both in the visible range and near‐infrared region. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Synthesis and characterization of novel electroactive polyamides and polyimides with bulky 4‐(1‐adamantoxy)triphenylamine moieties

A novel adamantoxytriphenylamine‐containing diamine monomer, 4‐(1‐adamantoxy)‐4′,4″‐diaminotriphenylamine, was synthesized from readily available reagents. Two series of novel electroactive aromatic polyamides and polyimides with bulky 4‐(1‐adamantoxy)triphenylamine moieties were prepared from the newly synthesized diamine monomer with various aromatic dicarboxylic acids and tetracarboxylic dianhydrides, respectively. All the resulting polyamides and most of the polyimides were readily soluble in polar organic solvents and could be solution cast into tough and flexible films. These polymers showed moderate to high glass transition temperatures in the range of 263–311 °C, and they were fairly stable up to a temperature above 480 °C (for polyamides) or 500 °C (for polyimides). Cyclic voltammograms of the polyamides and polyimides showed one pair of reversible redox waves with oxidation half‐wave potentials (E_1/2) in the range of 0.78–0.81 and 0.97–1.05 V, respectively, versus Ag/AgCl in an acetonitrile solution. In addition, the polymers were found to display stable electrochromic properties by repeated cyclic scans between 0.0 and 1.1–1.2 V, with coloration change from a colorless or pale yellowish neutral form to a dark blue or bluish green oxidized form. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1740–1755, 2009     

New electroactive and electrochromic aromatic polyamides with ether‐linked bis(triphenylamine) units

A new class of electroactive polyamides with ether‐linked bis(triphenylamine) [O(TPA)₂] units were prepared through the direct phosphorylation polycondensation from N,N‐di(4‐aminophenyl)‐N′,N′‐diphenyl‐4,4′‐oxydianiline and aromatic dicarboxylic acids. These polyamides were amorphous with good solubility in many organic solvents, such as NMP and DMAc, and could be solution‐cast into strong and flexible polymer films. Their decomposition temperatures (T_d) at a 10% weight‐loss in nitrogen and air were recorded at 556–568 °C and 537–555 °C, respectively. The glass‐transition temperatures (T_g) of all the polyamides were observed in the range of 218?253 °C by DSC. Cyclic voltammograms of the polyamide films cast onto an indium‐tin oxide (ITO)‐coated glass substrate exhibited two reversible oxidation redox couples at 0.80–0.82 V and 0.96–0.98 V versus Ag/AgCl in an electrolyte containing acetonitrile solution. The polyamide films showed excellent electrochemical and electrochromic stability, with a color change from a colorless or pale yellowish neutral form to green and purple oxidized forms at applied potentials ranging from 0 to 1.2 V. These polymers can also be used to fabricate electrochromic devices, and they showed high coloration efficiency, high redox stability, and fast response time. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 496–510     

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     

Lithium electrochromism of atmospheric pressure plasma jet-synthesized NiO x C y thin films

Reversible lithium intercalation and deintercalation behavior of atmospheric pressure plasma jet (APPJ)-synthesized organonickel oxide (NiO _x C _y ) thin films under various substrate distances is testified in an electrolyte (1?M LiClO₄–propylene carbonate solution) at low driving voltages from ?0.5 to 1.5?V. Fast responses of 2?s bleaching at ?0.5?V and 6?s coloration at +1.5?V are accomplished for the nano-porous NiO _x C _y thin films. This study reveals that a rapid synthesis of electrochromic NiO _x C _y thin films in a single process via APPJ by 21?s is investigated. This study presents a noteworthy electrochromic performance in a light modulation with up to 43% of transmittance variation and a coloration efficiency of 36.3?cm²/C at a wavelength of 830?nm after 200?cycles of cyclic voltammetry measurements.