Synthesis and chemical properties of electrochromic π‐conjugated polyphenylenes with pendant viologen‐TCNQ salts

Polyphenylene (PP) with NH₂ side groups, namely, PFluNH ₂ , was synthesized by the Pd‐catalyzed reaction of 2,5‐dibromoaniline with 9,9‐dihexylfluorene‐2,7‐diboronic acid bis(1,3‐propanediol) ester. The reaction of PFluNH ₂ with 1‐hexyl‐1′‐(2,4‐dinitrophenyl)‐4,4′‐bipyridinium diiodide ( SaltBPy(I^?) ) eliminated 2,4‐dinitroaniline to yield PPs with viologen (1,1′‐disubstituted 4,4′‐bipyridinium dications), PFluBPy(I^?) . The reaction of PFluBPy(I^?) with Li⁺TCNQ ^? resulted in anion exchange between Cl ^? and TCNQ ^? , and yielded PFluBPy(TCNQ^?) . The reaction of PFluBPy(TCNQ^?) with the neutral TCNQ⁰ resulted in an interaction between TCNQ ^? and TCNQ⁰, and yielded PFluBPy(TCNQ^?‐TCNQ⁰) . Cyclic voltammetry measurements suggested that an electrochemical reduction of the viologen moiety and oxidation of the polymer backbone within PFluBPy(TCNQ^?) and PFluBPy(TCNQ^?‐TCNQ⁰) . Furthermore, this reaction was accompanied by electrochromism. The electric conductivities (σ) of the pellets molded from PFluBPy(TCNQ^?) to PFluBPy(TCNQ^?‐TCNQ⁰) were 2.7 × 10 ^{? 4} and 4.2 × 10 ^{? 4} Scm ^{? 1}, respectively; these σ values were higher than that observed for PFluNH ₂ (σ < 10 ^{? 8} Scm ^{? 1}) due to the self‐doping in the polymers. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis and characterization of a ferrocene‐modified,polyaniline‐like conducting polymer

A novel monomer called 1,1′‐ferrocenediacyl anilide (FcA) was synthesized from ferrocene (Fc). Copolymerization was carried out between FcA and aniline (ANI) by an electrochemical method. The novel monomer and copolymer were characterized with ¹H‐NMR, Fourier transform infrared (FTIR) spectroscopy, and ultraviolet–visible (UV–vis) spectroscopy. The hydrogen protons of the benzene ring were moved to a low field in ¹H‐NMR, and the absorption band of N?Q?N (where Q is the quinoid ring) appeared in the FTIR spectrum of the polymer. The peaks of both Fc and the π–π* electronic transition in the UV–vis spectra were redshifted. The results indicate that the copolymer mainly existed as a highly delocalized conjugated system. X‐ray diffraction analysis established further proof, and the process of electrochemical deposition was observed by scanning electron microscopy. The optimal synthesis conditions of the copolymer were determined through changes in the monomer molar ratios and the scan rate. The ideal performance of the copolymer was gained when the monomer molar ratio between FcA and ANI was 1:4 and the scan rate was 50 mV/s. Furthermore, the electrochemical performances were tested in detail by cyclic voltammetry, galvanostatic charge–discharge testing, and electrochemical impedance spectroscopy. The results show that the specific capacitance of poly(1,1′‐ferrocenediacyl anilide‐co‐aniline) increased up to 433.1 F/g at 0.5 A/g, the diffusion resistance was very small, and the durability was good enough. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43217.     

Synthesis and spectroelectrochemistry of dithieno(3,2‐b:2′,3′‐d)pyrrole derivatives

New π‐conjugated polymers containing dithieno(3,2‐b:2′,3′‐d)pyrrole (DTP) were successfully synthesized via electropolymerization. The effect of structural differences on the electrochemical and optoelectronic properties of the 4‐[4H‐dithieno(3,2‐b:2′,3′‐d)pyrrol‐4‐yl]aniline (DTP–aryl–NH₂), 10‐[4H‐dithiyeno(3,2‐b:2′,3′‐d)pirol‐4‐il]dekan‐1‐amine (DTP–alkyl–NH₂), and 1,10‐bis[4H‐dithieno(3,2‐b:2′,3′‐d)pyrrol‐4‐yl] decane (DTP–alkyl–DTP) were investigated. The corresponding polymers were characterized by cyclic voltammetry, NMR (¹H‐NMR and ¹³C‐NMR), and ultraviolet–visible spectroscopy. Changes in the electronic nature of the functional groups led to variations in the electrochemical properties of the π‐conjugated systems. The electroactive polymer films revealed redox couples and exhibited electrochromic behavior. The replacement of the DTP–alkyl–DTP unit with DTP–aryl–NH₂ and DTP–alkyl–NH₂ resulted in a lower oxidation potential. Both the poly(10‐(4H‐Dithiyeno[3,2‐b:2′,3′‐d]pirol‐4‐il)dekan‐1‐amin) (poly(DTP–alkyl–NH₂)) and poly(1,10‐bis(4H‐dithieno[3,2‐b:2′,3′‐d]pyrrol‐4‐yl) decane) (poly(DTP–alkyl–DTP)) films showed multicolor electrochromism and also fast switching times (<1 s) in the visible and near infrared regions. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40701.     

Synthesis of two D‐π‐A polymers π‐bridged by different blocks and investigation of their photovoltaic property

The synthesis, characterization, photophysical and photovoltaic properties of two 5,6‐bis(octyloxy)benzo[c][1,2,5]thiadiazole‐containing wide‐band‐gap donor and acceptor D‐π‐A alternating conjugated polymers (HSD‐a and HSD‐b) have been reported. These two polymers absorb in the range of 300–700 nm with a band gap of about 1.88 and 1.97 eV. The HOMO energy levels were ?5.44 eV for HSD‐a and ?5.63 eV for HSD‐b. Polymer solar cells with HSD‐b :PC₇₁BM as the active layer demonstrated a power conversion efficiency (PCE) of 2.59% with a high V_oc of 0.93 V, a J_sc of 7.3 mA/cm², and a comparable fill factor (FF) of 0.38 under simulated solar illumination of AM 1.5G (100 mW/cm²) without annealing. In addition, HSD‐a :PC₇₁BM blend‐based solar cells exhibit a PCE of 2.15% with a comparable V_oc of 0.64 V, J_sc of 8.75 mA/cm^?2, and FF of 0.40. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41587.     

Synthesis of nitropyridine‐based π‐conjugated polymers and their chemical properties

π‐Conjugated poly(3‐nitropyridine‐2,5‐diyl) ( PPy‐3‐NO₂ ), poly(3,3′‐dinitro‐2,2′‐bipyridine‐5,5′‐diyl) ( PBpy‐3,3′‐diNO₂ ), and a poly(arylene ethynylene) type polymer consisting of a 3,3′‐dinitro‐2,2′‐bipyridine unit ( PAE‐1 ) were synthesized by Cu‐promoted Ullmann coupling reaction and Pd‐catalyzed coupling reaction. PPy‐3‐NO₂ and PAE‐1 were soluble in organic solvents such as DMSO, DMF, and chloroform, and gel permeation chromatography analysis showed a number average molecular weight (M_n) of 9,300 and 12,300, respectively. PPy‐3‐NO₂ gave intrinsic viscosity, [η], of 0.53 dL g^?1 in DMF. PBpy‐3,3′‐diNO₂ had somewhat lower solubility. The polymers exhibited a UV–vis peak at about 430 nm. PPy‐NO₂ received electrochemical reduction at ?1.5 V versus Ag⁺/Ag in acetonitrile, and gave an electrochemical redox cycle in a range from 0 to ?1.1 V versus Ag⁺/Ag in an aqueous solution. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1763–1767, 2006     

Nanostructured star‐shaped polythiophene with tannic acid core: Synthesis,characterization, and its physicochemical properties

For the first time, synthesis and characterization of a nanostructured star‐shaped polythiophene (PTh) with tannic acid core by both chemical and electrochemical oxidation polymerization methods through a “core‐first” method is reported. The chemical structures of all samples as representatives were characterized by means of Fourier transform infrared (FTIR), and ¹H nuclear magnetic resonance (NMR) spectroscopies. The electroactivity behaviors of the synthesized samples were verified under cyclic voltammetric conditions, and their conductivities were determined using the four‐probe technique. The synthesized star‐shaped PTh showed higher electrical conductivity and electroactivity than those of the PTh in both chemical and electrochemical polymerized samples, due to its large surface area, spherical, and three‐dimensional structure. Moreover, the thermal behaviors, optical properties, and morphologies of the synthesized samples were investigated by means of thermogravimetric analysis (TGA), ultraviolet–visible (UV–Vis) spectroscopy, and field emission scanning electron microscopy (FE‐SEM), respectively. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43513.     

Optical and electrochemical properties of oligo(1,5‐dialkoxynaphthalene‐2,6‐diyl)s with self‐assembled ordered structures in solid state

Oligo(1,5‐dialkoxynaphthalene‐2,6‐diyl)s were synthesized by Ni(cod)₂ (cod = 1,5‐cyclooctadiene)‐promoted condensation reactions of 1,5‐dialkoxy‐2,6‐dibromonaphthalenes. The UV–Vis, photoluminescence (PL), and powder X‐ray diffraction (XRD) measurements suggested that the oligomers have a self‐assembling ordered structure in the solid state. The oligomers underwent electrochemical oxidation (p‐doping), which occurred at lower potentials for films than for acetonitrile solutions containing [Et₄N]BF₄. This effect is caused by the longer π‐conjugation lengths of the oligomers in films, which was attributed to molecular self‐assembly leading to ordered structures in the solid state. The electrochemical reaction of the oligomers was accompanied by electrochromism. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41840.     

The electropolymerization of several poly(3‐methylthiophene) films in the same used solution and its consequence in their properties

The effect of the electropolymerization of seven poly(3‐methylthiophene) (P3MT) films in the same used monomer solution have been investigated. Cyclic voltammetry, UV‐visible, scanning electron microscopy, and electrochemical impedance measurements were carried out to understand the effect of the solution reusing on the polymer electrochemical properties. The obtained results show that, as the solution is reused, the polymerization rate increase and the charge in of the cyclic voltammetry decrease. Besides, there are important changes in the sample's morphologies, with the increase of the synthesis number, the amount of fibers increase and this leads to lower the conductivity of the polymer film. In agreement to this, the impedance data analysis shown important changes in the interfacial electronic parameters, i.e., changer transfer resistance and double‐layer capacitance, used to describe the films. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44368.     

Shielding and dielectric properties of sulfonic acid‐doped π‐conjugated polymer in 8.2–12.4 GHz frequency range

This article deals with dielectric and electromagnetic interference shielding properties of the polyaniline doped with dodecyl benzene sulfonic acid (DBSA) synthesized by microemulsion polymerization of aniline in aqueous solution of DBSA. Dielectric constant and shielding effectiveness due to absorption (SE_A) were calculated using S‐parameter obtained from the vector network analyzer in 8.2–12.4 GHz frequency range. Maximum SE_A of 26 dB (>99%) was achieved for polymer sample. The real part ε′ of complex permittivity shows small variation, whereas the imaginary part ε″ is found to decrease with the increase in frequency. Different formulations have been performed to see the effect of monomer to dopant ratio on intrinsic properties of polyaniline. Further characterization of polymer was carried out by UV–visible and thermal gravimetric analysis, whereas the conductivity measurements were carried out by the four‐probe method.© 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Electrodeposition of free‐standing poly(o‐dihydroxybenzene‐co‐3‐methylthiophene) films with tunable fluorescence properties

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     

Measurement of thermal properties of polyaniline/metal from room temperature to 170°C

The heat transfer through polyaniline (PANI) mixed with metals (manganese and iron) is studied by measuring its effective thermal conductivity (λ_e) and effective thermal diffusivity (χ_e) from room temperature to 170°C at normal pressure. Simultaneous measurements of the λ_e and χ_e values of samples A (100% Fe), B (50% Fe and 50% Mn), and C (100% Mn) of the PANI mixtures with different percentages of Fe and Mn are carried out using the transient plane source technique. It is observed that the λ_e and χ_e of the above samples are almost independent of the temperature in a range of temperatures. However, maximum values for the λ_e and χ_e are found for sample A at ～140°C, sample B at ～130°C, and sample C at ～120°C. An empirical relationship deduced from a polynomial fit of the experimental data is established for the temperature dependence of the λ_e and χ_e values of these samples. Reasonably good agreement is obtained between the theoretically predicted results and the experimental data. This behavior is explained on the basis of bond formation between the metals (Fe and Mn) and nitrogen of the PANI matrix. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 430–435, 2003     

Electropolymerization and properties of 3,4‐ethylenedioxythiophene backbone polymer with tetrathiafulvalene as pendant

Three 3,4‐ethylenedioxythiophene (EDOT) derivatives, including an EDOT‐tetrathiafulvalene (TTF) derivative, were synthesized by Steglich esterification of carboxylic acids with hydroxymethyl EDOT (3,4‐ethylenedioxythiophene methanol). The UV spectra showed that there was no distinctive intramolecular interaction for the EDOT–TTF monomer between the EDOT and the TTF moieties in the ground state; however, the cyclic voltammetry responses implied that such intramolecular interaction occurred. Electropolymerization in excessive potential could bring in strong overoxidation effects and degradation in the polymer film. The polymers were simulated using density functional theory with Gaussian03 package and the optimized HOMO and LUMO state were figured out. The conductivity of TTF‐polymer was 6 S·cm^?1 obtained by galvano station and 4.8 × 10^?3 S·cm^?1 obtained by potentiostatic electropolymerization after doping with 7,7,8,8‐tetracyanoquinodimethane. The results indicated that this polymer was a reasonable candidate for conducting materials and it was meaningful to increase the conductive dimensions of TTF polymers by chemical doping. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis and spectroelectrochemical investigation of low‐bandgap polymer: Integrated quinoxaline and benzimidazole in one electron acceptor unit

Two novel π‐conjugated monomers, 6‐(4‐octyloxyphenyl)‐4,8‐bis(thiophene‐2‐yl)‐3H‐[d] imidazole[1,2,5] benzothiadiazole (M3) and 4‐(4‐octyloxyphenyl)‐2,6‐bis(thiophene‐2‐yl)‐3H‐[d] imidazole‐acenaphtho[1,2‐b]quinoxaline (M4), were synthesized. The monomer M4 contains a thiophene electron‐donating unit and electron withdrawing unit in which quinoxaline and benzimidazole integrated in one benzene ring. Electrochemical polymerization of the monomers was carried out in acetonitrile/dichloromethane solvent mixture containing tetra‐n‐butylammonium hexafluorophosphate and electrochromic properties of polymers (P3 and P4) are described in this article. Furthermore, the effects of structural difference on electrochemical redox behavior and spectroelectrochemical properties of the two resulting polymers were examined. The results showed that an anodic wave at +0.48 V versus Ag wire pseudo‐reference electrode corresponding to the monomer M4 oxidation was observed, while one anodic wave at +0.70 V was observed in oxidation of M3 as it contains stronger electron withdrawing thiadiazole structure. The UV‐vis‐Near‐infrared (Near‐infrared spectroscopy) (NIR) spectra analysis revealed that the two polymers have one absorbance band centered at 603 nm. The band gaps, defined as the onset of the absorption band at 603 nm of these polymers, were determined as 1.60 eV for P3 and as 1.55 eV for P4. The electrochromic results showed that P3 revealed about 20% optical contrast at 980 nm and the P4 has 30% optical contrast at 806 nm with low response time (1 s for each polymer). © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40861.     

Synthesis and characterization of new conjugated soluble polythiophenes with excellent reversible electrochemical properties

A series of five new conjugated polythiophene (PT) derivatives containing piperidinyl groups as a side chain were synthesized by ferric trichloride oxidization. All of the polymers were soluble in common organic solvents, and their high regioregularity were confirmed by ¹H‐NMR. The weight‐average molar masses ranged from 5931 to 22,955 g/mol with a low polydispersity index ranging from 1.18 to 1.79. The fluorescence emission maximum of poly[3‐(N‐methyl propionate–4′‐piperidine)methylene–thiophene] in the films was 725 nm in the yellow–red region, higher than that of the other PT derivatives. All five polymers exhibited reversible p‐doping/dedoping (oxidation/reneutralization) processes; this indicated that these polymers could be applied in electrical equipment in the doping state. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Electrochemical copolymerization of carbazole and 3‐methylthiophene

The copolymerization of carbazole (CZ) and 3‐methylthiophene (3MeT) was successfully performed electrochemically in freshly distilled boron trifluoride diethyl etherate by direct anodic oxidation of the monomer mixtures, although the oxidation potentials of CZ and 3MeT were quite different. The electrochemical properties of the copolymers were studied with cyclic voltammetry. The influence of the applied polymerization potential on the synthesis of the copolymers was investigated. The higher potential favored the incorporation of 3MeT units into the copolymers. The insertion of 3MeT units into polycarbazole (PCZ) was helpful in improving the conductivity of PCZ. The novel copolymers had the advantages of both PCZ and poly(3‐methylthiophene), that is, good redox activity, good thermal stability, and high conductivity. The structure and morphology of the copolymers were investigated with ultraviolet–visible, infrared spectroscopy, thermal analysis, and scanning electron microscopy. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1877–1885, 2006     

Electrochemical and optical properties of dicyclohexylmethyl substituted poly(3,4‐propylenedioxythiophene) analogue

An analogue of disubstituted 3,4‐propylenedioxythiophenes, namely 3,3‐bis(cyclohexylmethyl)‐3,4‐dihydro‐2H‐thieno[3,4‐b][1,4]dioxepin (ProDOT‐CycHex₂), was synthesized and its electrochemical polymerization was carried out successfully in an electrolyte solution of 0.1 M tetrabutylammonium hexafluorophosphate dissolved in a mixture of acetonitrile and dichloromethane (3/1: v/v). The corresponding polymer called PProDOT‐CycHex₂ has a reduced band gap of 1.85 eV and an electrochromic property: blue/violet when neutralized and highly transparent when oxidized. Also, PProDOT‐CycHex₂ film exhibited faster response time (0.7 s) and higher coloration efficiency (769 cm²/C) during oxidation when compared to its benzyl substituted analogue. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46214.     

Synthesis of 3′,4′‐disubstituted terthiophenes. Characterization and electropolymerization. I. 3′,4′‐dibromo‐2,2′:5′,2″‐terthiophene in photovoltaic display

Recent studies on conducting polymers have demonstrated that polymers of 3‐substituted thiophene produce very stable compounds. Although this kind of substitution improves the regularity, structural defects still exist. To overcome this drawback, the polymerization of 3,4‐disubstituted thiophene is proposed as a convenient way of synthesizing regular, highly conjugated conductive polymers. Our interest is thus focused on the synthesis of tetra‐substituted thiophene derivatives, their polymerization, electrochemical properties, spectral characteristics, oxidizing potential, and the feasibility of photocells development. In this article, we report the synthesis and characterization of 3′,4′‐dibromo‐2,2′:5′,2″‐terthiophene which, as such or modified, may be a good starting product for obtaining new monomers of 3′,4′‐disubstituted terthiophenes, that would allow the effect of the substituents on the properties of the respective polymers to be studied. In addition, the monomer was electropolymerized and the resulting deposit was electrochemically and morphologically characterized. Two conclusions were drawn: first, more uniform and homogeneous layers than those of polythiophene are obtained; second, the thin layers of the polymer, electron acceptors, absorb in the visible. Finally, photocells were assembled to investigate their photovoltaic effect. Although the so prepared solar cells showed some photovoltaic effect, the yield was low.© 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5314–5321, 2006     

Optimization of thermoelectric properties of metal‐oxide‐based polymer composites

Thermoelectric modules can be used for thermal energy harvesting. Common rigid thermoelectric stacks usually contain heavy metal alloys such as Bi₂Te₃. In order to substitute conventional materials and to reduce manufacturing costs, nontoxic, inexpensive and abundant materials using low‐cost processes are first choice. This study deals with polymer composites consisting of a polysiloxane matrix filled with thermoelectric Sn_0.85Sb_0.15O₂ particles in micrometer scale. Thin composite sheets have been prepared by doctor blade technique and the Seebeck coefficient, the electrical and thermal conductivity, and the porosity were measured. Platelet‐type particles, consisting of Sn_0.85Sb_0.15O₂‐coated insulating mica substrate and globular Sn_0.85Sb_0.15O₂ particles have been varied in size, coating thickness and were mixed with each other in different ratios. The filler content was varied in order to maximize the figure of merit, ZT, to 1.9 × 10^?5 ± 4 × 10^?6. Owing to their low raw material costs and the high degree of design freedom of polymer composites, one may use these materials in thermoelectric generators for remote low‐power demanding applications. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2014 , 131, 40038.     

Low‐potential electrochemical polymerization of 6‐nitroindole and characterization of its polymers

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     

Specroelectrochemical,switching kinetics,and chronoamperometric studies of dibenzyl derivative of poly(3,4‐propylenedioxythiophene) thin‐film‐based electrochromic device

The dibenzyl derivative of poly(3,4‐propylenedioxythiophene) (PProDOT‐Bz₂) thin film is deposited onto ITO‐coated glass substrate by electropolymerization technique. The electropolymerization of ProDOT‐Bz₂ is carried out by a three‐electrode electrochemical cell. The cyclic voltammogram shows the redox properties of electrochemically prepared films deposited at different scan rates. The thin films prepared were characterized for its morphological properties to study the homogeniety. Classic six‐layer structure of PProDOT‐Bz₂ electrochromic device using this material was fabricated and reported for the first and its characterizations such as spectroelectrochemical, switching kinetics, and chronoamperometric studies are performed. The color contrast of the thin film and the device achieved are 64 and 40%, respectively, at λ_max (628 nm). The switching time is recorded and the observed values are 5 s from the coloring state to the bleaching state and vice versa. The chronoamperometry shows that the device performed up to 400 cycles, and it is capable of working up to 35 cycles without any degradation. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40717.