Two novel heterocycle-fluorene-heterocycle monomers, 2,2′-(9,9-dioctyl-9H-fluorene-2,7-diyl)dithiophene (Th-F-Th) and 5,5′-(9,9-dioctyl-9H-fluorene-2,7-diyl)bis(2,3-dihydrothieno[3,4-b][1,4]dioxine) (EDOT-F-EDOT), were synthesized via Stille coupling reaction and electropolymerized to form corresponding polymers P(Th-F-Th) and P(EDOT-F-EDOT). Furthermore, the optoelectronic properties of the obtained monomers and polymers were explored using cyclic voltammetry (CV), UV–vis, and emission spectra and in situ spectroelectrochemical techniques. The band gap values of monomers calculated by DFT were 3.75 eV for EDOT-F-EDOT and 4.03 eV for Th-F-Th, while that of P(EDOT-F-EDOT) and P(Th-F-Th) were brought down to 1.70 and 2.10 eV, respectively. Both polymers exhibited excellent redox activity and electrochromic performance. P(EDOT-F-EDOT) exhibited a maximum optical contrast of 25.8% at 500 nm in visible region with a response time of 1.2 s. In addition, the coloration efficiency of P(EDOT-F-EDOT) was calculated to be 220 cm² C⁻¹. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 325–334

3-Dodecylthiophene end-capped two monomers: 2,8-bis-(4-dodecyl-thiophen-2-yl)-dibenzothiophene (DBT-3DTh) and 2,8-bis-(4-dodecyl-thiophen-2-yl)-dibenzofuran (DBF-3DTh) were synthesized via Stille coupling reaction. Both monomers exhibited emission peaks at about 400 nm with fluorescence quantum yields ranging from 0.16 to 0.21. The corresponding electroactive polymers poly(2,8-bis-(4-dodecyl-thiophen-2-yl)-dibenzothiophene) (PDBT-3DTh) and poly(2,8-bis-(4-dodecyl-thiophen-2-yl)-dibenzofuran) (PDBF-3DTh) were obtained by electropolymerization method and displayed good electrochemical stability. Both polymers switched between light gray in the neutral state and blue in the oxidized state. Kinetic investigations showed that PDBT-3DTh exhibited a maximum optical contrast (ΔT %) of 25.23% at 575 nm with the coloration efficiency (CE) of 196 cm² C⁻¹. However, the electrochromic properties of PDBF-3DTh were inferior to PDBT-3DTh. Further detailed discussions with EDOT and 3-alkylthiophenes end-capped DBT/DBF hybrid electrochromic polymers were comparatively studied. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 1468–1478

Two poly(2'-aminomethyl-3,4-ethylenedioxythienylene) (PEDOT-MeNH₂) derivatives were successfully synthesized by electrochemical polymerization of precursors, diethyl 3'-(((2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl) methyl)azanediyl)dipropanoate (monomer 1) and ethyl 3-(((2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl) methyl)amino)propanoate (monomer 2), respectively. Structure–property relationships of monomers and polymers, including electrochemical, optical properties, and morphology, were systematically explored. Significantly, the designed polymers exhibited red and orange emission signatures with high fluorescence quantum yields (Φ_F) of 0.044 and 0.045 compared with those of monomers; they may be used as building blocks for rational design of fluorescent materials. Moreover, cyclic voltammetry and spectroelectrochemistry studies demonstrated that poly(diethyl 3'-(((2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methyl)azanediyl) dipropanoate) (P1) and poly(ethyl 3-(((2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methyl)amino) propanoate) (P2) can be reversibly oxidized and reduced accompanied by obvious color changes from light purple to light blue for P1, and from purple to blue for P2. Furthermore, both P1 and P2 displayed higher optical contrasts (40–70%) in the visible region, favorable coloration efficiency (typically 50–230 cm² C⁻¹). From these results, the two polymers would be promising candidate materials for display applications. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 2081–2091

Oligo(oxyethylene) chains cross-linked 2,2’-bithiophene (BT-E5-BT) has been synthesized successfully. A free-standing copolymer film based on BT-E5-BT and 3,4-ethylenedioxythiophene (P(BT-E5-BT-co-EDOT)) has been synthesized by electrochemical polymerization. The electrical conductivity of P(BT-E5-BT-co-EDOT) copolymer (16 S m⁻¹) has improved by four orders of magnitude compared to the homopolymer of BT-E5-BT (P(BT-E5-BT), 5 × 10⁻³ S m⁻¹) at room temperature. Both homopolymer and copolymer films exhibit well-defined redox and satisfied coloration efficiency. Spectroelectrochemistry studies indicate that the P(BT-E5-BT-co-EDOT) has a lower band gap in the range of 1.83–1.90 eV and shows more plentiful electrochromic colours (green, blue, purple and salmon pink) compared with the homopolymer P(BT-E5-BT). The Copolymer P(BT-E5-BT-co-EDOT) shows the moderate optical contrast (26% of 480 nm) and coloration efficiency (205.41 cm⁻¹ C⁻²). The copolymer method provides a novel way to fabricate a free-standing organic electrochromic device. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 1583–1592

The degree of oxidation of conducting polymers has great influence on their thermoelectric properties. Free-standing poly(3-methylthiophene) (P3MeT) films were prepared by electrochemical polymerization in boron trifluoride diethyl etherate, and the fresh films were treated electrochemically with a solution of propylene carbonate/lithium perchlorate as mediator. The conductivity of the resultant P3MeT films depends on the doping level, which is controlled by a constant potential from −0.5 to 1.4 V. The optimum electrical conductivity (78.9 S cm⁻¹ at 0.5 V) and a significant increase in the Seebeck coefficient (64.3 μV K⁻¹ at −0.5 V) are important for achieving an optimum power factor at an optimal potential. The power factor of electrochemically treated P3MeT films reached its maximum value of 4.03 μW m⁻¹ K⁻² at 0.5 V. Moreover, after two months, it still exhibited a value of 3.75 μW m⁻¹ K⁻², and thus was more stable than pristine P3MeT due to exchange of doping ions in films under ambient conditions. This electrochemical treatment is a significant alternative method for optimizing the thermoelectric power factor of conducting polymer films.

Poly(4-(((2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy)methyl)benzoic acid) (PEDOT-Ph-COOH) was facilely synthesized by the direct electropolymerization of 4-(((2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy)methyl)benzoic acid (EDOT-Ph-COOH) in CH₂Cl₂-Bu₄NPF₆ (0.10 M) system, and the PEDOT-Ph-COOH films were systematically investigated. The results displayed that the film had excellent reversible redox activities, good electrochemical performance, and rough and compact surface. Finally, the PEDOT-Ph-COOH film was used as an optical chemo-sensor for the highly selective and sensitive detection of F⁻, , , , Cu²⁺, and Fe³⁺ in dimethyl sulfoxide. Satisfactory results indicated that optical chemo-sensor based on PEDOT-Ph-COOH possessed an excellent sensing performance and enhanced optical response, and it might be as potential promising materials, such as electrochromic devices, supercapacitors and so on. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41559.

The rapid development of novel organic technologies has led to significant applications of the organic electronic devices such as light-emitting diodes, solar cells, and field-effect transistors. There is a great need for conducting polymers with high conductivity and transparency to act as the charge transport layer or electrical interconnect in organic devices. Poly(3,4-ethylenedioxythiophene): poly(styrenesulfonic acid) (PEDOT:PSS), well-known as the most remarkable conducting polymer, has this role owing to its good film-forming properties, high transparency, tunable conductivity, and excellent thermal stability. In this Review, various of interesting physical and chemical approaches that can effectively improve the electrical conductivity of PEDOT:PSS are summarized, focusing especially on the mechanism of the conductivity enhancement as well as applications of PEDOT:PSS films. Prospects for future research efforts are also provided. It is expected that PEDOT:PSS films with high conductivity and transparency could be the focus of future organic electronic materials breakthroughs.

As conventional organic solvents present inherent toxicity, deep eutectic solvents (DES) have been considered as excellent candidates due to their green characteristics. In this work, thermoelectric properties enhancement of PEDOT:PSS films is achieved by introducing DES as an additive and post-treatment reagent. Direct addition and post-treatment approaches lead to a maximum Seebeck coefficient of 29.1 μV K⁻¹ and electrical conductivity of 620.6 S cm⁻¹, respectively. In addition, an optimal power factor is obtained by DES post-treatment, reaching up to 24.08 μW m⁻¹ K⁻², which is approximately four orders of magnitude higher than the pure PEDOT:PSS. Assuming a thermal conductivity of 0.17 W m⁻¹ K⁻¹, the maximum ZT value is estimated to be 0.042 at 300 K. Further, atomic force microscopy and X-ray photoelectron spectroscopy are performed and suggest that the remarkably enhanced electrical conductivity originates from the removal of the excess insulating PSS and the phase separation between the PEDOT and PSS chains. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015, 53, 885–892

In this work, the asymmetrical analog of 3,4-ethylenedioxythiophene (EDOT), thieno[3,4-b]-1,4-oxathiane (EOTT), was synthesized and chemically polymerized first in aqueous solution using poly(styrene sulfonic sodium) (PSS) as the polyelectrolyte to yield poly(thieno[3,4-b]-1,4-oxathiane) (PEOTT)/PSS. As-formed film exhibited low electrical conductivity (∼10⁻⁴ S/cm). Alternatively, EOTT together with EDOT (in different molar ratio of 1:1 and 1:5) was copolymerized and the polymer poly(EOTT-co-EDOT)/PSS had electrical conductivity of 10⁻¹ S/cm. After dimethyl sulfoxide (DMSO) treatment, the electrical conductivity was enhanced to 10⁰ S/cm; however, the conductivity of the above homopolymer was reduced (∼10⁻⁵ S/cm). Raman spectroscopy was used to interpret conductivity enhancement or reduction after DMSO treatment. The conductivity decrease of PEOTT/PSS compared to poly(EOTT-co-EDOT)/PSS may arise from the conformational change of PEOTT backbone from the quasi-planar to the distorted planar mode induced by PSS^–/PSSH through ionic interaction. Kinetic studies revealed that the copolymer had high coloration efficiencies (375 cm²/C), low switching voltages (−0.8 to +0.6 V), decent contrast ratios (45%), moderate response time (1.0 s), excellent stability, and color persistence. An electrochromic device employing poly(3-methylthiophene) and poly(EOTT-co-EDOT)/PSS as the anode and cathode materials was also studied. From these results, poly(EOTT-co-EDOT)/PSS would be a promising candidate material for organic electronics. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015, 53, 2285–2297

Two new 3,4-ethylenedioxythiophene (EDOT) derivatives, (2R)-(2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methyl 2-phenylpropanoate ((R)-EDTM-PP) and (2S)-(2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methyl 2-phenylpropanoate ((S)-EDTM-PP), were synthesized and electropolymerized in dichloromethane (CH₂Cl₂) and terabutylammonium hexafluorophosphate (Bu₄NPF₆) system. As chiral electrodes, poly((2R)-(2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methyl 2-phenylpropanoate) ((R)-PEDTM-PP) and poly((2S)-(2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methyl 2-phenylpropanoate) ((S)-PEDTM-PP)-modified glassy carbon electrodes (GCEs) were employed to successfully recognize 3,4-dihydroxyphenylalanine (DOPA) enantiomers. Cyclic voltammetry presents that (R)-PEDTM-PP and (S)-PEDTM-PP had good redox activity and stability. Spectroelectrochemistry studies revealed (R)-PEDTM-PP and (S)-PEDTM-PP polymers have electronic bandgap of 1.68 and 1.66 eV, and could be reversibly oxidized and reduced accompanying with obvious color changes from dark blue to light purple. In addition, the electrochemical behavior, structural characterization, thermal stability, morphology and circular dichroism of (R)-PEDTM-PP and (S)-PEDTM-PP films were investigated in detail. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015, 53, 2238–2251

Chronoamperometry technique was used to prepare polypyrrole onto low alloy steel surface from aqueous solutions. The morphology and composition of the as-obtained deposit was characterized by scanning electron microscopy, X-ray diffraction, and Fourier-transform infrared techniques. The dendritic polymer could be realized at the high potential and favorable mass transfer conditions. Contact angle tests proved that the polypyrrole with rough surfaces had small contact angles. After the modification with the 1H, 1H, 2H, 2H-perfluorooctyl trichlorosilane, the values of contact angles of polypyrrole reached up to ca. 130°. The consequent infusion of perfluorinated lubricant into the hydrophobic matrix led to a composite material. Potentiodynamic polarization tests in 3.5 wt % NaCl solution revealed that low alloy steel covered with this composite material raised the corrosion potential more than 1000 mV and decreased the corrosion current density ca. 3 orders, suggesting that the perfluorinated lubricant/ polypyrrole composite material behaved as a good candidate for corrosion inhibition. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40184.

A novel strategy via paper as an effective substrate has been introduced as a thermoelectric material in this work. Free-standing poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS)/paper composite films are conveniently prepared by a one-step method of directly writing PEDOT:PSS solution on paper, making the process simple, rapid, and facile. The free-standing composite films display excellent flexibility, light weight, soaking stability in water, and great potential in large-scale production. Improved thermoelectric properties are obtained in PEDOT:PSS/paper composite films, owing to the simultaneously enhanced Seebeck coefficient (30.6 μV K⁻¹) and electrical conductivity, and a low thermal conductivity (0.16 W m⁻¹ K⁻¹) compared with pristine PEDOT:PSS films. The results indicate that paper as an effective substrate is suitable for the preparation of high-performance and flexible thermoelectric materials. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014, 52, 737–742

2-((2,3-Dihydrothieno[3,4-b]dioxin-2-yl)methoxy)methyl oxirane (EDOT-MO) was successfully synthesized by the reaction of epichlorohydrin with hydroxymethylated-3,4-ethylenedioxylthiophene (EDOT-MeOH), which was synthesized via a simple four-step sequence. Poly(hydroxymethylated-3,4-ethylenedioxylthiophene) (PEDOT-MeOH) and poly(2-((2,3-dihydrothieno[3,4-b]dioxin-2-yl)methoxy)methyl oxirane) (PEDOT-MO) were electrosynthesized through electropolymerization of EDOT-MeOH and EDOT-MO, respectively. Structural, electrochemical, optical, and thermal properties of as-formed polymers were investigated by FTIR, cyclic voltammetry, UV–vis, and thermogravimetry. Spectroelectrochemistry studies demonstrated that PEDOT-MeOH and PEDOT-MO could be reversibly oxidized and reduced accompany with obvious color changes. Further kinetic studies demonstrated that the introduction of hydroxymethyl or ethylene oxide group significantly improved electrochromic properties of 3,4-ethylenedioxythiophene (PEDOT) and resulted in high contrast ratios (57.3% at 585 nm) and coloration efficiencies (338.5 cm² C⁻¹), low switching voltages, and fast response time. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 1989–1999

The chemical oxidative copolymerization of 3,4-ethylenedithiathiophene (EDTT) with 3,4-ethylenedioxythiophene (EDOT) and 2′-hydroxymethyl-3,4-ethylenedioxythiophene in a poly(styrene sulfonic acid) aqueous solution was successfully carried out to form stable, dark blue colloidal dispersions in water. Coating these dispersions onto polypropylene substrates led to the formation of free-standing copolymer films. The mechanical, electrical, and thermoelectrical properties of these films were investigated; the films showed superior properties in comparison with those of poly(3,4-ethylenedithiathiophene) (PEDTT)/poly(styrene sulfonate) (PSS). The copolymer film based on EDTT and EDOT achieved a high electrical conductivity (8.2 × 10⁻² S cm⁻¹) at 298 K; this could be improved about 10 times through the addition of dimethyl sulfoxide (DMSO) or DMSO/isopropyl alcohol into the polymer dispersion with almost constant Seebeck coefficients of about 9 μV K⁻¹. On the contrary, these additives had almost no effect on the conductivity of PEDTT/PSS. The structure and morphology of the polymer films were studied by X-ray diffraction and SEM analyses. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013

Poly(2-chloromethyl-2,3-dihydrothieno[3,4-b][1,4]dioxine), a chloromethyl functionalized poly(3,4-ethylenedioxythiophene) derivative (PEDOT-MeCl), was synthesized electrochemically via the potentiostatic polymerization of its monomer in dichloromethane solution containing suitable tetrabutylammonium tetrafluoroborate, then it was used for the characterization of film properties and the fabrication of electrochemical sensor. The properties of the resulting PEDOT-MeCl film were characterized by different methods such as cyclic voltammetry, electrochemical impedance spectroscopy, Fourier transform infrared and ultraviolet–visible techniques, scanning electron microscope, and thermogravimetric analysis. The PEDOT-MeCl film displayed a good reversible redox activity, remarkable capacitance properties, good thermal stability, rough, and porous structure, especially fluorescent spectra indicated that PEDOT-MeCl was a blue-emitter with maximum emission centered at 396 and 398 nm. Finally, the PEDOT-MeCl film was employed for the fabrication of the sensing electrode, and dopamine was chosen as a model analyte for the application of the electrochemical sensor. Results indicated that the PEDOT-MeCl film as sensing interface was feasible, and studies of these film properties were very beneficial for studying properties and applications of other poly(3,4-ethylenedioxythiophene) derivative films. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 2660–2670, 2013

Relatively scant work was related to polynaphthalene (PN) and its derivatives because of the unique nonlinear optical properties which make PN and its derivatives owning potential applications in various domains. According to relevant studies, the pursuit for the synthesis of high quality PN films is a great challenge for the applications of PN. To achieve high quality polymer films, three bridged naphthalene derivatives were designed, and finally two crosslinked PN exhibiting space network were electrosynthesized, respectively, by direct anodic oxidation from 1,6-bis(naphthalen-2-yloxy)hexane and 1,4-bis((naphthalen-2-yloxy)methyl)benzene in mixed electrolyte of dichloromethane containing boron trifluoride diethyl etherate. Furthermore, as-formed conducting films were characterized by cyclic voltammetry, spectroscopic analysis, thermal analysis, and scanning electron microscopy. And the series of characterizations indicated that films hold high stability and good blue-light-emitting property. Meanwhile, these polymer films were smooth, shiny, and flexible easily being processed into various shapes by conventional mechanical methods. Consequently, these high quality PN films will facilitate their potential applications as blue-light-emitting materials in organic light-emitting diode. Because di(naphthalen-2-yl) terephthalate was difficult to electropolymerize, the effects of bridged spacers to polymerization were also discussed. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012

A novel precursor, 1,2-bis[6-(9H-carbazol-9-yl)hexyloxy] benzene (BCHB), was successfully synthesized. Its polycarbazole-functionalized polycatechol network films, poly{1,2-bis[6-(9H-carbazol-9-yl)hexyloxy] benzene} (PBCHB), with good redox activity were formed by the direct anodic oxidation of BCHB in CH₂Cl₂ and boron trifluoride diethyl etherate binary solvent solution. Ultraviolet–visible spectroscopy, Fourier transform infrared spectroscopy, ¹H-NMR, and matrix-assisted laser desorption ionization–time of flight mass spectrometry were used to characterize the polymers. The results indicate that the network polymers could be synthesized electrochemically with different polymerized units by controlled electropolymerization. The PBCHB films prepared at low potential were oligomers with short conjugation lengths and were soluble in common organic solvents, whereas the polymers with long conjugation lengths and hyperbranched network structures obtained at high potential were insoluble. The electrosynthesized polymers exhibited blue emission maxima around 450 nm and were much more redshifted than their monomer. The emissions were also brighter; this indicated the polymers are potential good blue-light emitters. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012

A novel semiconducting oligo(9-fluorenylideneacetic acid) (OFYA) with good redox activity and stability was successfully electrosynthesized by direct anodic oxidation of 9-fluorenylideneacetic acid (FYA) in CH₂Cl₂ containing boron trifluoride diethyl etherate (BFEE) as the supporting electrolyte. The as-formed OFYA film was readily soluble in dimethyl sulfoxide and tetrahydrofuran, and partly soluble in water, alcohol, acetonitrile and acetone. FT-IR and ¹H NMR spectra, together with computational results proved that FYA was probably polymerized through the coupling at C(2) and C(7) positions. Further, OFYA was a typical green light-emitter with maximal emission at 555 nm and its fluorescence quantum yield was distinctly improved in comparison with that of the monomer. The oligomer was also studied by UV-vis spectroscopy, MALDL-TOF mass spectrometry, and thermal analysis, respectively.

Systematic research on the synthesis, chemical oxidative polymerization of 3,4-ethylenedithiathiophene (EDTT) in the presence of surfactants or not, and solid-state polymerization of 2,5-dibromo-3,4-ethylenedithiathiophene (DBEDTT) and 2,5-diiodo-3,4-ethylenedithiathiophene (DIEDTT) under solventless and oxidant-free conditions has been investigated. Effects of oxidants (Fe³⁺ salts, persulfate salts, peroxides, and Ce⁴⁺ salts), solvents (H₂O, CH₃CN/H₂O, and CH₃CN), surfactants, and so forth on polymerization reactions and properties of poly(3,4-ethylenedithiathiophene) (PEDTT) were discussed. Characterizations indicated that FeCl₃ was more suitable oxidant for oxidative polymerization of EDTT, while CH₃CN was a better solvent to form PEDTT powders with higher yields and electrical conductivities. Dispersing these powders in aqueous polystyrene sulfonic acid (PSSH) solution showed better stability and film-forming property than sodium dodecylsulfate and sodium dodecyl benzene sulfonate. Oxidative polymerization of EDTT in aqueous PSSH solutions formed the solution processable PEDTT dispersions with good storing stability and film-forming performance. Solvent treatment showed indistinctive effect on electrical conductivity of free-standing PEDTT films. As-formed PEDTT synthesized from solid-state polymerization showed similar electrical conductivity, poorer stability, but better thermoelectric property than oxidative polymerization. Contrastingly, PEDTT synthesized from DIEDTT showed higher electrical conductivity (0.18 S cm⁻¹) than DBEDTT which showed better thermoelectric property with higher power factor value (6.7 × 10⁻⁹ W m⁻¹ K⁻²). © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012

Electrochemical copolymerization of o-dihydroxybenzene (oDHB) and 3-methylthiophene (3MeT) was successfully achieved in boron trifluoride diethyl etherate by direct anodic oxidation of the monomer mixtures, although the oxidation potentials of oDHB and 3MeT were quite different. The influence of the applied polymerization potential on the synthesis of the copolymers was investigated. The higher applied potential favored the incorporation of 3MeT units into the copolymers. The structure and properties of the copolymers were investigated with UV-vis spectroscopy, fluorescence spectroscopy, FTIR spectroscopy, and thermal analysis. The novel copolymers had many advantages, including good redox activity, good thermal stability, and high electrical conductivity. Additionally, the copolymers fluorescence properties that were tunable through changes in the feed ratio of the monomer mixtures. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010

High quality poly(p-phenylene) (PPP) film with conductivity of 0.015 S cm⁻¹ was synthesized electrochemically by direct anodic oxidation of p-terphenyl (PP) oligomers in boron trifluoride diethyl etherate (BFEE) containing 37.5% CH₂Cl₂ (v/v). The oxidation onset potential of PP in this medium was measured to be only 1.23 V vs. saturated calomel electrode (SCE), which was lower than that determined in CH₂Cl₂ + 0.1 mol L⁻¹ Bu₄NBF₄ (1.87 V vs. SCE). As-formed PPP films showed good electrochemical behavior, good electrochromic property and good thermal stability. The structures and morphology of doped and dedoped PPP were investigated by UV-vis, FTIR, and Scanning electron micrographs. The infrared spectroscopic measurements for the estimation of chain lengths revealed that PPP was composed of about 10 phenyl rings. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010

A novel high-quality polyphenanthrene (PPH) film with electrical conductivity of 10⁻¹ S cm⁻¹ was synthesized electrochemically by direct anodic oxidation of phenanthrene in boron trifluoride diethyl etherate containing 10% concentrated sulfuric acid (v/v). The oxidation onset potential of phenanthrene in this medium was measured to be only 0.91 V versus saturated calomel electrode (SCE), which was lower than that determined in acetonitrile + 0.1 mol L⁻¹ Bu₄NBF₄ (1.56 V versus SCE). As-formed PPH films from this medium showed good electrochemical behavior and stability. De-doped PPH films were thoroughly soluble in dimethylsulfoxide or CHCl₃. The structure and morphology of the polymer were investigated using UV-visible and Fourier transform infrared (FTIR) spectroscopy and scanning electron microscopy. FTIR and ¹H NMR spectra showed that the PPH was grown via the coupling of the monomer mainly at the C₄, C₅, C₉ and C₁₀ positions. Fluorescence spectral studies indicated that PPH was a blue-green light emitter. Copyright © 2007 Society of Chemical Industry

High-quality polycarbazole (PCz) films with an electrical conductivity of 10⁻² S·cm⁻¹ were synthesized electrochemically by direct anodic oxidation of carbazole in a novel mixed electrolyte of acetic acid containing 26% boron trifluoride diethyl etherate (BTDE) and 5% poly(ethylene glycol) with molar mass of 400 (by volume). The oxidation potential of carbazole in this medium was measured to be only 0.89 V vs. a saturated calomel electrode (SCE), which was much lower than that determined in acetonitrile containing 0.1 mol·L⁻¹ Bu₄NBF₄ (1.36 V vs. SCE). PCz films obtained from this medium showed good electrochemical behavior, good thermal stability, and were partly soluble in strong polar organic solvents such as dimethyl sulfoxide and tetrahydrofuran. The fluorescence spectra implied that PCz obtained from this medium was a good blue-light emitter. FT-IR, ¹H NMR and theoretical studies showed that the polymerization of carbazole mainly occurred at the 3,6-positions. To the best of our knowledge, this is the first report on the electrosyntheses of conducting polymers in mixed electrolyte of acetic acid and BTDE.

Conducting polymers bearing nitro substituents are very important from both academic and industrial viewpoints. However, it is very difficult to electrosynthesize such conducting polymers because of the strong electron-withdrawing effect of nitro groups. In this article, we describe the electrochemical synthesis of films of a new conducting polymer, high-quality poly(6-nitroindole) (P6NI), by direct anodic oxidation of 6-nitroindole in boron trifluoride diethyl etherate containing 10% (v/v) diethyl ether. The oxidation potential onset of 6-nitroindole in this medium has been measured to be just 0.98 V versus a saturated calomel electrode (SCE), which is much lower than that determined in acetonitrile containing 0.1 mol/L tetrabutylammonium tetrafluoroborate (1.6 V vs SCE). Thermal studies have revealed that P6NI displays good thermal stability. The electrical conductivity of the P6NI films has been measured to be 0.08 S/cm. Structural studies have shown that the polymerization of the 6-nitroindole ring occurs mainly at the 2,3-positions. Fluorescence spectral studies have shown that the principal excitation and emission peaks of P6NI are at 416 and 535 nm, respectively, with a fluorescence quantum yield of 0.05. All these properties of P6NI films may facilitate their potential applications in various fields, such as electrochemical sensors and green-light-emitting materials. To the best of our knowledge, this is the first report on the electrosynthesis and characterization of 6-nitro-substituted polyindole films. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008

High-quality freestanding and conducting poly[3-(6-bromohexyl)thiophene] (PBHT) films with electrical conductivity of 20 S/cm were synthesized electrochemically by direct anodic oxidation of 3-(6-bromohexyl)thiophene (BHT) in boron trifluoride diethyl etherate (BFEE). The oxidation potential of BHT in pure BFEE was measured to be only 1.2 V versus saturated calomel electrode, SCE much lower than that determined in acetonitrile (ACN) (1.8 V vs SCE). The polymer films obtained from this media were very shiny and flexible and can be easily cut into various shapes. The structure and morphology of the polymer films were investigated by UV-vis, infrared, ¹H-NMR spectroscopy, thermal analysis, and scanning electron microscopy (SEM). All these results indicated that the terminal bromide did not have negative effect on the electrochemical polymerization of BHT. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008