Electrochromic properties of a novel low band gap conductive copolymer

A copolymer of 2,5-di(thiophen-2-yl)-1-p-tolyl-1H-pyrrole (DTTP) with 3,4-ethylene dioxythiophene (EDOT) was electrochemically synthesized. The resultant copolymer P(DTTP-co-EDOT) was characterized via cyclic voltammetry, FTIR, SEM, conductivity measurements and spectroelectrochemistry. Copolymer film has distinct electrochromic properties. It has four different colors (chestnut, khaki, camouflage green, and blue). At the neutral state λ_max due to the π-π^* transition was found to be 487 nm and E_g was calculated as 1.65 eV. Double potential step chronoamperometry experiment shows that copolymer film has good stability, fast switching time (less than 1 s) and good optical contrast (20%).An electrochromic device based on P(DTTP-co-EDOT) and poly(3,4-ethylenedioxythiophene) (PEDOT) was constructed and characterized. The device showed reddish brown color at −0.6 V when the P(DTTP-co-EDOT) layer was in its reduced state; whereas blue color at 2.0 V when PEDOT was in its reduced state and P(DTTP-co-EDOT) layer was in its oxidized state. At 0.2 V intermediate green state was observed. Maximum contrast (%ΔT) and switching time of the device were measured as 18% and 1 s at 615 nm. ECD has good environmental and redox stability.     

High glass transition and thermal stability of new pyridine-containing polyimides: Effect of protonation on fluorescence

A new diamine monomer containing heterocyclic pyridine and triphenylamine groups, 4-(4,4′-diaminotriphenylamine)-2,6-bis(4-methylphenyl)pyridine (4), was synthesized by Chichibabin and nucleophilic fluoro-displacement reactions. The diamine was used to prepare a series of novel polyimides via polycondensation with various aromatic tetracarboxylic dianhydrides in N-methyl-2-pyrrolidinone. The polyimide 4a derived from the diamine 4 with 4,4′-hexafluoroisopropylidenediphthalic anhydride and having high T_g (313 °C), mechanical, and thermal properties was soluble in various organic solvents, such as N-methyl-2-pyrrolidinone, N,N-dimethylacetamide, N,N-dimethylformamide, pyridine, chloroform, tetrahydrofuran, at room temperature. The polyimide (4a) could be cast into a self-standing film from DMAc solution and was thermally converted into tough and flexible film. The film had high tensile modulus of 2.2 GPa and exhibited excellent thermal stability in both nitrogen and air (T_d¹⁰ > 550 °C). The pristine polymer exhibited the UV-vis absorption bands in the region 240-400 nm and protonated polymer exhibited absorption in the region 390-500 nm. The protonated polymer possessed strong orange fluorescence (around 600 nm) in THF solution after protonation with acids as excited at 438 nm. The fluorescent intensity was influenced by the acid concentrations and the chemical structure of conjugated bases. The fluorescent intensity at 600 nm increased as acid concentration from a lower to a moderate concentration and decreased at higher concentrations.     

Synthesis of a soluble conjugated copolymer based on dialkyl-substituted dithienothiophene and its application in photovoltaic cells

A soluble conjugated alternating 3,5-didecanyldithieno[3,2-b:2′,3′-d]thiophene-thiophene copolymer was synthesized by palladium(0)-catalyzed Stille coupling reaction. The thermal, absorption, emission, electrochemical, and photovoltaic properties of the polymer were examined. A weight-average molecular weight around 6.2 × 10⁴ and a polydispersity index of 1.8 was estimated for the polymer using gel permeation chromatography. The polymer exhibits good thermal stability with decomposition temperature of 340 °C and glass-transition temperature of 136 °C. The polymer shows strong absorption peaked at 505 nm in diluted solution and 518 nm in thin film with an optical band gap 2.0 eV. The polymer exhibits intense emission located at 550 nm in solution and 603 nm in film. The HOMO and LUMO energies of the polymer were estimated to be −5.4 and −3.4 eV, respectively, by cyclic voltammetry. Polymer solar cells were fabricated based on the blend of the polymer and methanofullerene [6,6]-phenyl C61-butyric acid methyl ester (PCBM). The power conversion efficiency of 0.7% was achieved under AM 1.5, 100 mW/cm² using polymer:PCBM (1:4, w/w) as active layer.     

Unobstructed electron transfer on porous polyelectrolyte nanostructures and its characterization by electrochemical surface plasmon resonance

Thin organic films with desirable redox properties have long been sought in biosensor research. We report here the development of a polymer thin film interface with well-defined hierarchical nanostructure and electrochemical behavior, and its characterization by electrochemical surface plasmon resonance (ESPR) spectroscopy. The nano-architecture build-up is monitored in real time with SPR, while the redox response is characterized by cyclic voltammetry in the same flow cell. The multilayer assembly is built on a self-assembled monolayer (SAM) of 1:1 (molar ratio) 11-ferrocenyl-1-undecanethiolate (FUT) and mercaptoundecanoic acid (MUA), and constructed using a layer-by-layer deposition of cationic poly(allylamine hydrochloride) (PAH) and anionic poly(sodium 4-styrenesulfonate) (PSS). Electron transfer (ET) on the mixed surface and the effect of the layer structures on ET are systematically studied. Under careful control, multiple layers can be deposited onto the 1:1 FUT/MUA SAM that presents unobstructed redox chemistry, indicating a highly ordered, extensively porous structure obtained under this condition. The use of SPR to trace the minute change during the electrochemical process offers neat characterization of local environment at the interface, in particular double layer region, allowing for better control over the redox functionality of the multilayers. The 1:1 SAM has a surface coverage of 4.1 ± 0.3 × 10⁻¹⁰ mol cm⁻² for ferrocene molecules and demonstrates unperturbed electrochemistry activity even in the presence of a 13 nm polymer film adhered to the electrode surface. This thin layer possesses some desirable properties similar to those on a SAM while presenting ∼15 nm exceedingly porous structure for high loading capacity. The high porosity allows perchlorate to freely partition into the film, leading to high current density that is useful for sensitive electrochemical measurements.     

Pure color and stable blue-light emission-alternating copolymer based on fluorene and dialkoxynaphthalene

A new blue-light emitting polymer that alternates between fluorene and alkoxynaphthalene structure has been developed. The fluorene and naphthalene units were highly distorted with an angle of 76.22° according to theoretical calculations. The obtained polymer has a weight average molecular weight of 273,800 with a polydispersity index of 2.35, good solubility and high thermal stability with a T_g of 176 °C. The film photoluminescence (PL) spectrum (405 nm) is consistent with that of solution and the PL spectra of the polymer did not show any peak in the long wavelength region even after annealing for 24 h at 100 °C. The double-layered device with an ITO/PEDOT/polymer/LiF/Al structure has a turn-on voltage of about 5.4 V, maximum brightness of 110 cd/m² and an electroluminescent efficiency of 0.09 cd/A. The OLED generates pure blue EL emission (λ_max = 405 nm) with excellent CIE coordinates (x = 0.15, y = 0.10) as well as stable blue EL emission that is not altered by voltage increase.     

Synthesis and electroluminescence properties of a novel tetraphenylsilane-oxadiazole-diphenyl(para-tolyl)amine polymer

A novel triarylaminooxadiazole-containing tetraphenylsilane light-emitting polymer (PTOA) has been synthesized. Excellent thermal stability was observed due to the presence of a rigid tetraphenylsilane-based polymer backbone (T_g = 218 °C, T_d = 373 °C). In solution, PTOA shows photoluminescence (PL) with an emission maximum at 426 nm, which is attributed to the light-emitting unit of the triarylaminooxadiazole group. In solid film, the emission maximum of PL is observed at 458 nm, a 32 nm red-shift from the PL in solution. The solvatochromic effect and excimer formed in the solid film are responsible for the red-shifting and broadening of the PL emission band. The PL stability and morphology of the PTOA solid film were further investigated by thermal annealing at elevated temperatures. No significant difference in the PL spectra or morphology was observed between a pristine sample and a repeatedly thermally annealed film (at 200 °C). PTOA-based PLED shows EL with a main peak at 458 nm accompanied by a shoulder at around 530 nm. The light emission from electromer or electroplex leads to a broadening of the EL spectra (400-650 nm), which corresponds to the interaction between the oxadiazole and diphenyl(4-tolyl)amine groups in different polymer segments or chains. A sky blue emission (Commission Internationale de L'Eclairage (CIE_x,y) coordinates (0.20,0.23)) was obtained for PTOA-based PLED. The brightness and efficiency of the PLED can be as high as 248 cd/m² and 0.54 cd/A, respectively. The EL of PTOA-based PLED has been further improved by blending the PTOA with poly(n-vinylcarbazole) (PVK) in different concentrations. The effects of concentration on the PL and EL were studied for the PTOA-PVK composite film-based PLEDs.     

A novel multichromic copolymer via electrochemical copolymerization of (S)-1,1′-binaphthyl-2,2′-diyl bis(N-(6-hexanoic acid-1-yl) pyrrole) and 3,4-ethylenedioxythiophene

Copolymer based on (S)-1,1′-binaphthyl-2,2′-diyl bis(N-(6-hexanoic acid-1-yl) pyrrole) (BPL) and 3,4-ethylenedioxythiophene (EDOT) is electrochemically synthesized and characterized. The comonomers exhibit relatively closer onset oxidation potentials, implying that the electrochemical copolymerization is relatively easy to be achieved. Electrochemical methods, FTIR, ¹H NMR and UV-vis analysis confirm that the resulting polymer is a copolymer rather than a blend or a composite of the respective homopolymers. Spectroelectrochemical analysis reveals that the copolymer film has distinct electrochromic properties from that of the BPL homopolymer film and shows six different colors under various potentials. At the neutral state of the copolymer, the π → π* transition absorption peak is located at 535 nm and E_g is calculated as 1.78 eV. The copolymer film shows a maximum optical contrast (ΔT%) of 31% and a switching time of 1.2 s which are higher and faster than those of the homopolymer of BPL (PBPL, 7.8% and 2 s). The new multichromic copolymer is thermally stable up to 345 °C and is electrochemically stable up to 1.39 V. SEM images illustrate that the copolymer film presents a much smoother surface than that of the respective homopolymers.     

The mediation reaction between the external couple Ferri/Ferrocyanide and Os(II) bipyridile poly-vinylpyridile films coated onto glassy carbon electrodes

The oxidation-reduction of the Ferri/Ferrocyanide couple in solution onto modified glassy carbon Rotating Disk Electrodes (RDE) covered by Os(II) bipyridile poly-vinylpyridile (OsBPP) polymer was studied at room temperature. Steady state polarization curves were carried out as a function of the rotation speed, the polymer thickness and the concentration of redox centers within the polymer. This system has the characteristic that the formal redox potentials of both the external redox couple (E⁰′(Fe(CN)₆^3−/4−) = + 0.225 V vs. SCE) and the mediator polymer (E⁰′(OsBPP) = 0.260 V vs. SCE) lie very close. It is demonstrated that diffusion of the Ferri/Ferrocyanide inside the polymer can be ruled out. Since the processes of charge transfer at the metal/polymer and the mediating reaction are fast, the experimental results can be interpreted in terms of a kinetics in which the charge transport in the polymer or the diffusion in the solution may be the rate determining step, according to the experimental conditions. A simple model is considered that allows interpreting the experimental results quantitatively. Application of this model allows the determination of the diffusion coefficient of the electrons within the film, D_e ≈ 10⁻¹⁰ cm² s⁻¹.     

Electrochemically synthesized nano size copolymer, poly (aniline-co-ethyl 4-aminobenzoate) and its spectroelectrochemical studies

Electroactive conducting copolymers of aniline (ANI) and ethyl 4-aminobenzoate (EAB) were prepared electrochemically. Cyclic voltammetric studies were carried out with different feed concentration of EAB on glassy carbon electrode surface. The voltammograms exhibited different behavior for different concentrations of EAB. The copolymers exhibited high solubility in many polar solvents. The scan rate exerted good influence on the polymer effect on this GCE copolymer film, revealing electroactive film’s excellent adherent properties. The effect of pH on the copolymer film showed that the polymer was electrochemically active up to pH 7.0. Spectroelectrochemical analysis of the copolymer film, carried out on an indium tin oxide (ITO) plate, showed multicolor electrochromic behavior when the applied potential was changed. The color of the copolymer was changed from neutral yellow (422 nm) to green (760 nm) and to blue (600 nm) at the concentration of 0.1 M aniline and 0.1 M EAB in 0.1 M H₂SO₄ medium. The copolymer was characterized by FT-IR spectral data. The surface morphology were studied using SEM and TEM analysis. The grain size of the copolymer was measured using XRD studies and was found to be 80 nm. The electrical conductivity of the copolymer was 3.21 × 10⁻² S cm⁻¹, as determined using a four-probe conductivity meter.     

Poly(thienylene-benzothiadiazole-thienylene-vinylene): A narrow bandgap polymer with broad absorption from visible to infrared region

Poly(thienylene-benzothiadiazole-thienylene-vinylene) (PTBTV) has been synthesized by Pd-catalyzed Stille-coupling method. The polymer shows broad absorption from visible to infrared region. The maximum absorption of PTBTV in solution and film state is at 600 nm and 614 nm, respectively. The absorption edge of PTBTV film is at 813 nm, indicating a narrow bandgap of 1.50 eV. The HOMO and LUMO energy levels of PTBTV are −4.99 eV and −3.49 eV, respectively. Polymer solar cell based on the blend of PTBTV as donor and [70] PCBM as acceptor was fabricated, the power conversion efficiency of the device is 0.51% under the illumination of AM1.5, 100 mW/cm².     

Preparation and reversible photo-crosslinking/photo-cleavage behavior of 4-methylcoumarin functionalized hyperbranched polyester

A novel hyperbranched polymer endcapped with 4-methylcoumarin group (MCTH40) was prepared via thiol-ene addition reaction of thiol-modified hyperbranched polyester (fully thioglycolic acetate of Boltorn™ H40, TAH40) with a vinyl monomer (7-(4-vinyl-benzyloxyl)-4-methylcoumarin, VBMC), and characterized with ¹H NMR and FT-IR spectroscopies. Its reversible photo-crosslinking/photo-cleavage behavior was evaluated based on the UV-vis spectroscopic analysis, and compared with the linear polymer, poly(7-(4-vinyl-benzyloxyl)-4-methylcoumarin (PVBMC)). The absorbance at 319 nm in the UV-vis spectrum gradually decreased under UVA irradiation (λ_max = 365 nm), and then rapidly recovered under UVC irradiation (λ_max = 254 nm). The fluorescence intensity of MCTH40 (λ_max = 469 nm) recovered to 85.2% of original level after photo-cleavage under UVC irradiation, higher than 83.5% of PVBMC (λ_max = 472 nm). The UV-vis analysis results indicated that MCTH40 performs more rapid photo-response than linear PVBMC under the same conditions. Furthermore, the average doses of UVA irradiation for the maximum degree of photo-crosslinking were 22.08 J cm⁻² for MCTH40 and 28.29 J cm⁻² for PVBMC. The average UVC doses of complete photo-cleavage were 9.44 J cm⁻² for MCTH40 and 9.58 J cm⁻² for PVBMC. The GPC analysis indicated that the average molecular weight and its PDI of MCTH40 showed a slight increase after three reversible cycles.     

Studies of a novel conducting polymer by cyclic and square wave voltammetries: Its synthesis and characterization

A novel conducting polymer of polynaphthidine, poly(NAP), was synthesized electrochemically by direct anodic oxidation of naphthidine in aqueous media. The yield of the electropolymerization reaction depends on the temperature and pH of the solution. It was possible to differentiate two working regions: I (for pH < 0.5 and all temperatures) where the film yield tends to zero and II (for approximately 2.0 < pH < 2.8 and temperatures >15 °C) where the film production is maximum. Therefore, the naphthidine electrooxidation mechanism was studied under experimental conditions of region I by cyclic (CV) and square wave voltammetries (SWV) as well as by controlled potential electrolysis.The experimental conditions of region II were chosen to obtain the poly(NAP). The electrochemical response of the film was investigated in pH 1 HClO₄ + 0.1 M NaClO₄ electrolyte solution by CV and SWV. A plot of I_p,n/fvs. f from SW voltammograms showed the so-called “quasi-reversible maximum”. Formal potential, formal rate constant and anodic transfer coefficient for the surface redox process were also evaluated from the SWV.The poly(NAP) is insoluble in common organic solvents and shows electrochromic behaviour. Its probable structure was determined by FTIR spectroscopy.     

Synthesis and photophysics of new highly luminescent poly(alkylthiophene) derivatives with pyridine in the backbone

Starting from 2,6-bis-(3-octylthiophene-2yl)-pyridine, two new poly(alkylthiophene) derivatives, POTPyOT and POTPy, containing pyridine in the backbone were prepared from nickel(0)-mediated Stille coupling or by palladium-catalyzed Yamamoto coupling. These polymers exhibited good solubility in common organic solvents, thermal stability up to 400 °C, and facile film formation. They were amorphous and give strong luminescence both in CHCl₃ solution and solid state film. The polymers emitted blue light in solution with photoluminescence (PL) emission maximum at 420-484 nm and green light with PL emission maximum at 500-514 nm in thin films. These polymers showed a reversible redox reaction at potential from 0 to 1.3 V (vs. SCE). Nevertheless, the reduced form of the polymer was very unstable; it decomposed in the presence of oxygen or water. The emission and UV-vis absorption of the polymer were influenced by the solvent polarity, protonation, and acid-base treatment. These may be the results of the stabilization of the polar excited state by solvation and the change of the conformation in polymer backbone. Electroluminescence (EL) was achieved from a single-layer PLED with the configuration of ITO/POTPyOT/Al. The turn-on voltage of the device is 10 V and the λ_max (550 nm) of the EL is voltage independent.     

A novel conjugated polymer based on cyclopenta[def]phenanthrene backbone with spiro group

Poly(2,6-(4,4-bis(2-ethylhexyl)-4H-cyclopenta[def]phenanthrene)) (PCPP) is a stable blue light emitting conjugated polymer even after annealing at 150 °C or operation of the device in air. The spiro form of PCPP, poly(2,6-(3′,6′-bis(2-ethylhexyloxy)-4,4′-spirobi(4H-cyclopenta[def]phenanthrene))) (spiro-PCPP), has been synthesized by Yamamoto polymerization. The PL emission spectrum of the polymer in THF solution shows a maximum peak at 398 nm, nearly identical with that of PCPP. The PL spectrum of the polymer in the solid state exhibits a maximum peak at 451 nm, which is red-shifted over 50 nm from that of the solution, due to the inter-chain interaction of the polymers. The PL spectra of spiro-PCPP in the mixture of THF and MeOH from 9:1 to 3:7 ratios showed increasing peaks at 458 and 484 nm. With an increased ratio of the hydrophilic solvent (MeOH), the inter-chain interaction of the hydrophobic polymers was enhanced to show peaks at 458 and 484 nm. This phenomenon has the same tendency as compared to the PL spectrum in solid thin film state. The polymer LED with the configuration of ITO/PEDOT/spiro-PCPP/Ca:Al emitted light with maximum peaks at around 463 nm. The emission color of the spiro-PCPP device is sky blue with the CIE coordinates of (0.14, 0.15), which are close to those of the standard blue (0.14, 0.08).     

Photoinduced reorientation and polarization holography in photo-cross-linkable liquid crystalline polymer films with large birefringence

A new photo-cross-linkable liquid crystalline polymer (PLCP) comprised 4-methoxycinnamoyloxy groups connected with a bistolane side group was synthesized to investigate thermally enhanced photoinduced molecular reorientation of a thin film with linearly polarized (LP) 365 nm light exposure. Due to the axis-selective photoreaction of the cinnamate groups followed by the thermally induced self-organization, large molecular reorientation parallel to the polarization of LPUV light (S > 0.6) and large birefringence at the non-resonance region (Δn = 0.34 at 632.8 nm) were obtained. The obtained Δn value is the largest among transparent PLCPs in the visible region. The influence of the degree of photoreaction and the annealing temperature on the thermally enhanced molecular reorientation behavior was explored in detail. Finally, for an application of thin optical devices using the PLCP films, pure polarization holographic gratings with large birefringence, which showed periodic molecularly oriented structure, were fabricated using a 325 nm He-Cd laser in various polarization modes and characterized their optical properties.     

Electrochemically and electrochromically stable polyimides bearing tert-butyl-blocked N,N,N′,N′-tetraphenyl-1,4-phenylenediamine units

A new class of electrochemically active polyimides with di-tert-butyl-substituted N,N,N′,N′-tetraphenyl-1,4-phenylenediamine units was prepared from N,N-bis(4-aminophenyl)-N′,N′-bis(4-tert-butylphenyl)-1,4-phenylenediamine and various aromatic tetracarboxylic dianhydrides via a conventional two-step procedure that included a ring-opening polyaddition to give poly(amic acid)s, followed by chemical or thermal cyclodehydration. Most of the polyimides are readily soluble in many organic solvents and can be solution-cast into tough and amorphous films. They had useful levels of thermal stability, with relatively high glass-transition temperatures (276-334 °C), 10% weight-loss temperatures in excess of 500 °C, and char yields at 800 °C in nitrogen higher than 60%. Cyclic voltammograms of the polyimide films cast on the indium-tin oxide (ITO)-coated glass substrate exhibited two reversible oxidation redox couples at 0.70-0.74 V and 1.05-1.08 V vs. Ag/AgCl in acetonitrile solution. The polyimide films revealed excellent stability of electrochromic characteristics, with a color change from colorless or pale yellowish neutral form to green and blue oxidized forms at applied potentials ranging from 0.0 to 1.3 V. These anodically coloring polymeric materials exhibited high optical contrast of percentage transmittance change (Δ%T) up to 44% at 413 nm and 43% at 890 nm for the green coloration, and 98% at 681 nm for the blue coloration. After over 50 cyclic switches, the polymer films still exhibited good redox and electrochromic stability.     

Phase separation and dewetting in polystyrene/poly(vinyl methyl ether) blend thin films in a wide thickness range

Phase separation and dewetting processes of blend thin films of polystyrene (PS) and poly(vinyl methyl ether) (PVME) in two phase region have been studied in a wide film thickness range from 65 μm to 42 nm (∼2.5R_g, R_g being radius of gyration of a polymer) using optical microscope (OM), atomic force microscope (AFM) and small-angle light scattering (LS). It was found that both phase separation and dewetting processes depend on the film thickness and were classified into four thickness regions. In the first region above ∼15 μm the spinodal decomposition (SD) type phase separation occurs in a similar manner to bulk and no dewetting is observed. This region can be regarded as bulk. In the second region between ∼15 and ∼1 μm, the SD type phase separation proceeds in the early stage while the characteristic wavelength of the SD decreases with the film thickness. In the late stage dewetting is induced by the phase separation. In the third region between ∼1 μm and ∼200 nm the dewetting is observed even in the early stage. The dewetting morphology is very irregular and no definite characteristic wavelength is observed. It is expected that the irregular morphology is induced by mixing up the characteristic wavelengths of the phase separation and the dewetting. In the fourth region below ∼200 nm the dewetting occurs after a long incubation time with a characteristic wavelength, which decreases with the film thickness. It is considered that the layered structure is formed in the thin film during the incubation period and triggers the dewetting through the capillary fluctuation mechanism or the composition fluctuation one.     

Synthesis and electrochemical characterization of bis(3,4-ethylene-dioxythiophene)-(4,4′-dinonyl-2,2′-bithiazole) comonomer

The synthesis and characterization of a novel donor acceptor donor type bis(3,4-ethylene-dioxythiophene)-(4,4′-dinonyl-2,2′-bithiazole) comonomer and its electrochemically prepared polymer on carbon fiber, Pt button and ITO plate is reported in this paper. Cyclic voltammetry of the polymer in 0.1 M Et₄NBF₄/CH₂Cl₂ exhibits a very well defined and reversible redox processes and this co-monomer can be either p-doped or n-doped. The half-wave oxidation potentials of the polymer (E_1/2) were observed at 0.303 and 0.814 V versus Ag/AgCl. The polymer is electrochromic; the onset for the π-π^* transition (E_g) of 1.75 eV with a λ_max at 2.15 eV and the homogeneous and high quality film of the polymer is stable of its optical properties offering fast switching time which is less than 0.25 s. The morphological studies reveal that the polymer was deposited as a continuous and very well adhering film to surface of the carbon fiber microelectrode. All these properties make this polymer favorable for use in electronic devices.     

Facile electrosynthesis of nitro-group-substituted oligopyrene with bicolored emission

Nitro-group-substituted oligopyrene (ONP) film with fairly high electrical conductivity (1.25 × 10⁻¹ S cm⁻¹) and good thermal stability was electrochemically synthesized by direct anodic oxidation of its monomer 1-nitropyrene (NP) in boron trifluoride diethyl etherate (BFEE). The oxidation potential of NP in this medium was determined to be 1.12 V vs. SCE, which was lower than that in acetonitrile +0.1 mol L⁻¹ Bu₄NBF₄ (1.27 V vs. SCE). ONP films obtained from this medium showed good redox activity and structural stability in both BFEE and concentrated sulfuric acid. Fourier transform infrared spectra and theoretical calculations showed that the electropolymerization of the NP monomer mainly occurred at the C(3), C(6) and C(8) positions. The fluorescence spectra suggested that soluble ONP emits strong blue or green fluorescence when excited at 402 nm or 504 nm, respectively. Scanning electron microscopy showed that highly crystalline nitro-group-substituted oligopyrene was formed on the electrode surface. All these results indicate that as-prepared ONP film has many potential applications in various fields.     

Redox behavior and optical response of nanostructured poly(3,4-ethylenedioxythiophene) films grown in a camphorsulfonic acid based micellar solution

Poly(3,4-ethylenedioxythiophene) (PEDOT) films have been electropolymerized from an aqueous micellar solution comprising camphorsulfonic acid (CSA), lithium trifluoromethanesulfonate (LiCF₃SO₃) and EDOT. The inclusion of the dopants CS⁻ and CF₃SO₃⁻ in the polymer structure and an unusually high doping level of 0.54 have been ascertained by the X-ray photoelectron spectroscopy. Transmission electron microscopy and atomic force microscopy studies show that the micellar effect of CSA leads to a morphology wherein polymer particles link together to form elongated shapes and also endows the film with a surface roughness of 25-30 nm. These nanostructures permit a facile intercalation-deintercalation of anions in the film during redox cycling. Electrochemical impedance spectroscopy show that the charge transfer phenomenon at the PEDOT-electrolyte interface is dominant in the high frequency region and diffusion controlled ionic movement prevails in the low frequency regime. The use of these films as potential cathodes in electrochromic windows is rationalized not only on the basis of their high scalability and ease of processing but also due to their large coloration efficiency (123 cm² C⁻¹) and transmission modulation (50%) at a photopic wavelength of 550 nm. But further improvement in color-bleach kinetics and reproducibility of redox behavior is desirable to broaden their spectrum of utility.