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A series of fluorinated poly (ether imide)s (PEIs) were prepared from asymmetry, bulky featured of 1,2-bis(3,4-dicarboxyphenoxy)-4-tert-butylbenzene dianhydride and various trifluoromethyl-based bis(ether amine)s via conventional thermal (H) or chemical (C) imidization. All fluorinated PEIs exhibited flexible, good mechanical properties and excellent solubility in a variety of organic solvents. In addition, the chemical imidization based PEI thin films showed cut-off wavelengths of UV-vis absorptions below 380 nm with very low yellowness index (b* < 5.5). They also exhibited high thermal stability with the 10 % weight loss temperature from 486 to 550 °C of in nitrogen or air atmosphere. Compared with the corresponding PEIs based on non-fluorinated bis(ether amine)s, fluorinated PEIs not only showed higher optical transparency, lower dielectric constants and water absorptions but also maintained thermal and mechanical properties.

Two triarylamine derivatives, DPPA-2(NHCO-TPA) and DPPA-2(NHCO-NPC), composed of a central diphenylpyrenylamine (DPPA) unit via amide groups linked to two triphenylamine (TPA) or N-phenylcarbazole (NPC) sides are developed as an electroactive precursor to prepare electrochromic films through electrochemical polymerization. The dilute solutions of these two DPPA-containing compounds showed notable fluorescence and solvatochromic shifts. Electroactive polymeric films could be electrodeposited on the ITO electrode surface by repetitive cyclic voltammetry scanning of their dichloromethane solutions containing dissolved 0.1 M tetrabutylammonium perchlorate (TBAP) between 0 and 1.5 V. The polymer films displayed multi-staged redox processes and color changes upon electrochemical oxidation. Spectroelectrochemistry and electrochromic switching stability of the polymers were investigated. Simple single-layer electrochromic devices were also fabricated and tested.

Four starburst molecules with a triphenylamine (TPA) core through the amide group linked to the terminal triphenylamine or (N-phenyl)carbazole (NPC) unit, coded as T-3(NHCO-TPA), T-3(NHCO-NPC), T-3(CONH-TPA), and T-3(CONH-NPC), were synthesized and their electrochemistry and electropolymerization were investigated. The oxidation potential and the stability of the oxidized forms of the starbursts are affected by the orientation of amide linkage and the structure of terminal triarylamine unit. Robust polymeric films could be built onto ITO/glass surface by repetitive cyclic voltammetry (CV) of the T-3(NHCO-TPA) solution containing an electrolyte. The electrodeposited films exhibited reversible electrochemical processes and strong color changes upon electro-oxidation, which can be switched by potential modulation. The electrochromic behavior of the film was clearly interpreted on the basis of spectroelectrochemical studies. T-3(CONH-TPA) did not undergo electropolymerization effectively. T-3(CONH-NPC) also could electrochemically polymerize to polymer films upon repeated CV scans. However, their electrochromic switching stability is less than that of the polymer film from T-3(NHCO-TPA).

N,N′-Bis(4-diphenylaminophenyl)pyromellitimide (TPA-PMDI) was synthesized from the condensation reaction of 4-aminotriphenylamine with pyromellitic dianhydride (PMDA). The triphenylamine-diimide TPA-PMDI could be electrochemically polymerized into ambipolar, redox-active polyimide films on the electrode surface in an electrolyte solution via the coupling reactions between triphenylamine radical cations. The electro-generated polyimide films (coded as PI-E) exhibit reversible redox processes and stable color changes upon electro-oxidation, changing from a colorless neutral form to orange-yellowish and blue oxidized states. The film could also display pale green and pink cathodic coloring upon electro-reduction. Electrochromic devices using the electropolymerized film as an active layer were also fabricated as preliminary investigations for electrochromic applications. For a comparative study, a structurally similar polyimide (PI-C) was prepared by a conventional two-step condensation from N,N′-bis(4-aminophenyl)-N,N′-diphenyl-4,4′-biphenyldiamine with PMDA, and its spectroscopic, electrochemical and electrochromic properties were compared with those of the electro-synthesized PI-E.

Novel electroactive triphenylamine-based polyamide (PA) films with a purposeful porous structure have been designed and prepared by a simple route. Polymer thin films containing well dispersed electrolyte salts were prepared first, then channels of pores could be generated within the polymer film by washing the salts out. With the help of the porous channels, the diffusion rate between electroactive species and the electrolyte during the electrochemical process could be effectively increased. Consequently, the driving potential and electrochromic response time can be efficiently improved through this approach. Novel porous PA films with optimal results both in optical transparency and electrochemical properties could be readily obtained by choosing a commonly used supporting electrolyte TBABF4 as a salt in this study. When the PA films containing un-washed TBABF4 salt were further assembled into electrochromic devices (ECDs), the salt could then be leached out during the electrochemical redox switching process to form a porous film structure and also serves as a supporting electrolyte in ECDs simultaneously. Therefore, EC performance such as the driving potential and response time could be enhanced obviously by this simplified fabrication procedure of ECDs.

Three bis(triphenylamine) diimides, TPA-PMDI, TPA-NTDI and TPA-PTDI, were synthesized from condensation of 4-aminotriphenylamine with pyromellitic dianhydride (PMDA), 1,4,5,8-naphthalenetetracarboxylic dianhydride (NTDA) and 3,4,9,10-perylenetetracarboxylic dianhydride (PTDA), respectively. Redox-active poly(arylamine-imide) films coded with TPA-PMPI, TPA-NTPI, and TPA-PTPI could be electrodeposited robustly on the electrode surface in an electrolyte solution via the oxidative coupling reactions between TPA radical cations. The CVs of these elecrtrodeposited films showed an ambipolar redox behavior, with a reversible redox couple at E1/2 of 0.99–1.02 V during the anodic scanning and two pairs of redox waves during cathodic scanning. The polyimide films exhibited multicolored anodic and cathodic coloring. Electrochromic devices using the electropolymerized films as active layers were also fabricated as preliminary investigations for electrochromic applications.

A robust polyimide film was facilely fabricated on the ITO-glass substrate from the electrolyte solution of a bis(triphenylamine) perylene diimide by electrochemical polymerization. The cyclic voltammogram of the electrodeposited polyimide film shows ambipolar redox processes, with a reversible redox couple with a half wave potential (E1/2) of + 0.99 V during the anodic scanning and two pairs of redox waves at E1/2 = − 0.41 V and − 0.65 V during cathodic scanning. The electroactive film did not delaminate from the electrode upon cycling electrochemically between its oxidized/reduced and neutral states. The polyimide film exhibits stable anodic and cathodic coloring, with high optical contrast, high coloration efficiency, and good cycling stability.

A diimide-dicarboxylic acid (DIDA) (I) was prepared from the condensation reaction of trimellitic anhydride (TMA) and 3,4′-oxydianiline (3,4′-ODA) in a 2:1 molar ratio, and another new tetraimide-dicarboxylic acid (TIDA) (II) was synthesized by condensation from 4,4′-(hexafluoroisopropylidene)diphthalic anhydride (6FDA), TMA, and 3,4′-ODA in a 1:2:2 molar ratio. Two series of aromatic poly(amide-imide)s (PAI) IVa-k and Va-k were synthesized by Yamazaki phosphorylation polyamidation reactions of DIDA I and TIDA II, respectively, with various aromatic diamines. Due to highly random segmental sequence for both series in the polymer chain and the incorporation of 6FDA moieties for the V series, all the polymers were readily soluble in many organic solvents and could be casted into transparent, flexible, and tough films with good mechanical properties. Glass-transition temperature (Tgs) of the IV series and V series were recorded in the range of 242–274°C and 264–295°C. In addition, almost all the poly...

Two N-phenylcarbazole and triphenylamine end-capped, 2,7-bis(diphenylamino)naphthalene-cored dicarboxamides were prepared by the condensation reactions from N,N′-bis(4-aminophenyl)-N,N′-bis(4-methoxyphenyl)-2,7-naphthalenediamine with two equivalent amount of N-(4-carboxyphenyl)carbazole and 4-carboxytriphenylamine, respectively. These two dicarboxamides can be electropolymerized into electroactive films on the electrode surface in an electrolyte solution via the oxidative coupling reactions between the terminal arylamino groups. The electro-generated polymer films exhibited reversible electrochemical oxidation processes and strong color changes upon electro-oxidation, which can be switched by potential modulation. The electrochromic films did not delaminate from the electrode surface upon cycling electrochemically between their neutral and oxidized states.

Four new fully triphenylamine-based polyamides coded as polyamide (CF3,CF3), polyamide (CF3,CH3), polyamide (CH3,CF3), and polyamide (CH3,CH3) were synthesized by the phosphorylation polyamidation reaction from various combinations of 3,5-bis(trifluoromethyl)-4′,4″-dicarboxytriphenylamine, 3,5-dimethyl-4′,4″-dicarboxytriphenylamine, 3,5-bis(trifluoromethyl)-4′,4″-diaminotriphenylamine, and 3,5-dimethyl-4′,4″-diaminotriphenylamine. All the polyamides were amorphous and readily soluble in many common organic solvents and could be solution-cast into transparent, flexible, and strong films with good mechanical properties. They had useful levels of thermal stability associated with high glass-transition temperatures of 268–287°C and 10 wt%-loss temperatures in excess of 500°C. Cyclic voltammograms of the film of polyamide (CH3,CH3) on the indium-tin oxide-coated glass substrates exhibited two oxidation redox couples with E1/2 around 0.82 and 1.29 V vs. Ag/AgCl in tetrabutylammonium perchlorate/acetonit...

New fluorine-containing, triphenylamine-based diamine and dicarboxylic acid monomers, namely 3,5-bis(trifluoromethyl)-4’,4”-diaminotriphenylamine (3a) and 3,5-bis(trifluoromethyl)-4’,4”-dicarboxytriphenylamine (3b), were synthesized and polymerized with commercially available aromatic dicarboxylic acids and diamines, respectively, leading to two series of aromatic polyamides 5a–h and 7a–e. Most of the polyamides were amorphous and readily soluble in many common organic solvents and could be solution-cast into transparent, flexible, and strong films with good mechanical properties. The polyamides had useful levels of thermal stability associated with high glass-transition temperatures of 273–305 °C and 10% weight-loss temperatures in excess of 500 °C. Cyclic voltammograms of the films of polymers 5a–h on the indium-tin oxide (ITO)-coated glass substrates exhibited reversible oxidation redox couples with E1/2 around 1.15 V versus Ag/AgCl in tetrabutylammonium perchlorate/acetonitrile solution, accompanied by a color change from colorless neutral state to reddish brown oxidized state. The 7 series polymers displayed a higher oxidation potential and less electrochemical stability as compared to the 5 series analogues.

A new 2,7-bis(diphenylamino)naphthalene-based diamine monomer, N,N′-bis(4-aminophenyl)-N,N′-bis(4-methoxyphenyl)-2,7-naphthalenediamine, was synthesized and polymerized with various aromatic dicarboxylic acids via the phosphorylation polyamidation reaction leading to a new series of redox-active and electrochromic aromatic polyamides. The polyamides exhibited high solubility in many polar aprotic solvents, good film-forming ability, and high thermal stability. They also showed stable electrochemical stability and anodically green coloring when oxidized. The two arylamino centers showed a weak electronic interaction via the 2,7-naphthalenediyl bridge, and thus they started to oxidize almost at the same time. No intervalence charge transfer (IVCT) absorption was observed during the oxidation processes of these polyamides. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 1409–1421

Two series of novel redox-active polyimides 8a–8f and 9a–9f were prepared through a conventional two-step procedure from six commercially available tetracarboxylic dianhydrides with 3,5-bis(trifluo...

A new triphenylamine-based diamine monomer 4,4′-diamino-4″-(1-piperidinyl)triphenylamine was synthesized and polymerized with various aromatic dicarboxylic acids via the phosphorylation polyamidation technique leading to a series of redox-active aromatic polyamides (aramids). All the aramids exhibit good solubility in many organic solvents and can be solution-cast into flexible and strong films with high thermal stability. Cyclic voltammograms of the polymer films on the indium-tin oxide (ITO)-coated glass substrate exhibit a pair of well-defined and reversible oxidation waves with very low onset potentials of 0.27–0.35 V (vs. Ag/AgCl) in acetonitrile solution, with a strong color change from colorless neutral form to green and deep blue oxidized forms in the range of 0.75–1.20 V. The optical transmittance change (Δ%T) at 636 nm between the neutral state and the fully oxidized state is up to 83%.

We report the synthesis and characterization of two carbazole-endcapped monomers, namely 2,8-di(carbazol-9-yl)dibenzothiophene ( SCz ) and 2,8-di(carbazol-9-yl)dibenzothiophene S,S -dioxide ( SO 2 Cz ), and their derived polymers PSCz and PSO 2 Cz prepared by both FeCl 3 oxidative coupling and electropolymerization processes. The dilute solutions of PSCz and PSO 2 Cz prepared by chemical oxidative coupling exhibited fluorescent and solvatochromic behavior. Thin polymeric films could be robustly electrodeposited onto the surface of the ITO-glass substrate by repetitive cyclic voltammetry scanning of monomers SCz and SO 2 Cz in an electrolyte solution between 0 and 1.8 V. The electrochemically generated polymer films exhibited two reversible oxidation redox couples due to successive oxidations of the biscarbazole unit. These polymer films also revealed good electrochemical and electrochromic stability, with coloration change from a colorless neutral state to yellow, green and blue oxidized states. Switching ability of the polymers was evaluated by kinetic studies upon measuring the percent transmittance (%T) at their maximum contrast point, indicating that the polymers exhibit moderate electrochromic performance.

In the past decade, a large number of high-performance polymers (HPPs) derived from triphenylamine (TPA) and/or carbazole groups have been synthesized, reported, and fabricated for electrochromic (EC) applications. HPPs such as aromatic polyamides and polyimides are well known for several remarkable properties such as outstanding thermal stability, chemical resistivity, and mechanical properties. Moreover, unlike most of the cathodically EC materials, arylamine-based HPPs can not only be colorless in the neutral form but also are not sensitive to oxygen/moisture and display excellent EC stability, all of which are also beneficial for practical application. The main aim of this chapter is to provide a comprehensive overview that covers the majority of work in the recent decade regarding arylamine-based EC HPPs and to demonstrate how the structural design influences the corresponding EC properties.

New triphenylamine-based aromatic diamine and dicarboxylic acid monomers, namely 3,5-dimethyl-4′,4″-diaminotriphenylamine (3a) and 3,5-dimethyl-4′,4″-dicarboxytriphenylamine (3b), were successfully synthesized by well-established procedures. Two series of novel aromatic polyamides 5a–5h and 7a–7e with 3,5-dimethyltriphenylamine units were prepared respectively from phosphorylation condensation of 3a with commercially available aromatic dicarboxylic acids and from 3b with commercially available aromatic diamines. Almost all the polyamides were amorphous and could be solution-cast into flexible, transparent, and tough films. All the polyamides exhibited useful levels of thermal stability, such as high glass-transition temperatures of 245–322 °C, 10% weight-loss temperatures in excess of 500 °C, and char yields at 800 °C in nitrogen higher than 63%. Cyclic voltammograms of the 5 series polyamides exhibited a reversible oxidation wave with E1/2 around 0.95 V versus Ag/AgCl in acetonitrile solution. The polymer films revealed excellent stability of electrochromic characteristics, with a color change from neutral state pale yellowish to green doped form at applied potentials ranging from 0 to 1.25 V.

Two triphenylamine-based diamine monomers, 4,4′-diamino-4″-methyltriphenylamine and 4,4′-diamino-4″-(trifluoromethyl)triphenylamine, were synthesized via the cesium fluoride-mediated double N-arylation reactions of p-toluidine and p-(trifluoromethyl)aniline, respectively, with p-fluoronitrobenzene, followed by palladium-catalyzed hydrazine reduction of the dinitro intermediates. New redox-active aromatic polyamides containing main-chain triphenylamine unit with methyl or trifluoromethyl ( CF3) group on the pendent phenyl ring were prepared by the phosphorylation polycondensation reactions of the synthesized diamine monomers with commercially available aromatic dicarboxylic acids. The polyamides were readily soluble in polar organic solvents and could afford flexible and strong films via solution casting. Cyclic voltammograms of the polyamide films cast onto the indium-tin oxide (ITO)-coated glass substrate revealed reversible electrochemical oxidation processes accompanied with color change from pale yellow to dark golden or green. Comparative studies of the methyl and CF3 substituents on the properties of the polyamides, such as solubility, thermal, electrochemical and electrochromic properties, are investigated.

Two series of new redox-active aromatic polyimides with methyl- (–CH3) or trifluoromethyl (–CF3)-protecting triphenylamine moieties were prepared from 4,4′-diamino-4″-methyltriphenylamine and 4,4′-diamino-4″-(trifluoromethyl)triphenylamine with aromatic tetracarboxylic dianhydrides via the conventional two-step polycondensation technique. Flexible and strong polyimide films could be obtained via the thermal curing of their precursor poly(amic acid) films or direct solution cast from some organosoluble polyimides. The polyimides showed high glass-transition temperatures between 269°C and 312°C, and they did not show significant decomposition before 500°C in air or under nitrogen atmosphere. Cyclic voltammograms of the polyimide films on the indium–tin oxide-coated glass substrate exhibited a pair of reversible redox waves with half-wave oxidation potentials of 1.08–1.10 V (for the –CH3 series) and 1.23–1.26 V (vs. silver/silver chloride; for the –CF3 series) in acetonitrile solution. The polyimide films showed anodic electrochromism from pale yellow neutral state to purplish blue (for the –CH3 series) and chrome yellow (for the –CF3 series) when oxidized.

Novel electroactive aromatic poly(amine-amide)s and poly(amine-imide)s with 4-fluorotriphenylamine units in the backbone were prepared from a newly synthesized diamine monomer, 4,4′-diamino-4″-fluorotriphenylamine, with aromatic dicarboxylic acids and tetracarboxylic dianhydrides via the phosphorylation technique and conventional two-step polycondensation technique, respectively. All the synthesized polymers could afford flexible and tough films with moderately high thermal stability. Cyclic voltammograms of the poly(amine-amide) and poly(amine-imide) films on the indium-tin oxide (ITO)-coated glass substrate exhibited a pair of reversible oxidation waves with oxidation half-wave potentials ( E 1/2 ) of 0.91–0.99 V and 1.19–1.23 V ( vs . Ag/AgCl), respectively, in an electrolyte/acetonitrile solution. They also exhibited obvious electrochromic behavior between their neutral and oxidized states changing from pale yellow to green or blue.

A series of new electroactive aromatic polyimides with (1-piperidinyl)triphenylamine moieties were prepared from 4,4′-diamino-4″-(1-piperidinyl)triphenylamine and aromatic tetracarboxylic dianhydrides via the conventional two-step polycondensation technique. Flexible and strong polyimide films could be obtained via the thermal curing of their precursor poly(amic acid) films. The polyimides showed high glass transition temperatures between 288°C and 318°C, and they did not show significant decomposition before 500°C in air or nitrogen atmosphere. Cyclic voltammograms of the polyimide films on the indium–tin oxide-coated glass substrate exhibited a pair of reversible oxidation waves with low onset oxidation potentials of 0.45–0.49 V (vs. silver/silver chloride) in acetonitrile solution. Upon oxidation, the color of the polyimide films changes from pale yellow to yellowish green and finally to blue.

Two novel electropolymerizable monomers, namely 3,5-bis(4-diphenylaminobenzamido)-N-[4-(carbazol-9-yl)phenyl]benzamide (5) and 3,5-bis(4-diphenylaminobenzamido)-N-[4-(3,6-dimethoxycarbazol-9-yl)phenyl]benzamide (5-MeO), were synthesized, and their electrochemical properties were studied by cyclic voltammetry. The electron-withdrawing amide groups efficiently blocked the radical cations delocalization between the two terminal TPA groups, rendering the electropolymerization of the TPA groups feasible. The polymer electrodeposited from monomer 5 could be further crosslinked through electro-coupling of the carbazole groups, which showed both electrochromic and fluorescent properties (the emission of blue light (460 nm) in solid state). Both of the electro-generated polymer films derived from 5 and 5-MeO showed reversible electrochemical oxidation processes in the range of 0 − 1.4 V with strong color changes and high contrast ratios in the visible and NIR regions upon electro-oxidation. © 2016 The Authors. Journal of Polymer Science Part A: Polymer Chemistry Published by Wiley Periodicals, Inc. 2016, 54, 2476–2485

A series of electroactive aromatic polyimides with (4-morpholinyl)triphenylamine units in the backbone were prepared from a newly synthesized diamine monomer, 4,4′-diamino-4″-(4-morpholinyl)triphenylamine, and aromatic tetracarboxylic dianhydrides via the conventional two-step polycondensation technique. Flexible and tough polyimide films could be obtained via the thermal curing of their precursor poly(amic acid) films. The polyimides showed high glass-transition temperatures ( T g ) between 290–313 °C, and they did not show significant decomposition before 500 °C in air or nitrogen atmosphere. Cyclic voltammograms of the polyimide films on the indium-tin oxide (ITO)-coated glass substrate exhibited a pair of reversible oxidation waves with low onset oxidation potentials of 0.43–0.53 V (vs. Ag/AgCl) in acetonitrile solution. They also exhibited multicolor electrochromic behavior between their neutral and oxidized states changing from pale yellow to cyan and bluish purple.

In order to gain deeper insight into the linkage effect and donor–acceptor effect on memory behavior (from DRAM to WORM), 4-(N-carbazolyl)triphenylamine-based polyimides and polyamides t-butyl-6FPI, t-butyl-DSPI, OMe-6FPI, OMe-DSPI, t-butyl-6FPA, t-butyl-DSPA, OMe-6FPA, and OMe-DSPA were synthesized and their memory behaviours were investigated.

Two compounds with a tri-carbazole (3Cz) structure, namely 3,6-di(carbazol-9-yl)-N-(4-nitrophenyl)carbazole (NO2-3Cz) and 3,6-di(carbazol-9-yl)-N-(4-aminophenyl)carbazole (NH2-3Cz), were synthesized and electropolymerized into robust polymer films on the electrode surface in an electrolyte solution via the oxidative coupling reactions. The electro-generated polymer films exhibited reversible electrochemical oxidation processes, with significant electrochromic behaviour. The colour of P(NO2-3Cz) films changed from the pale yellow neutral state to yellow-green as a radical cation and then to blue when fully oxidized. Upon oxidation, the colour of P(NH2-3Cz) films changed from colourless to pale green and finally to blue. Furthermore, we also synthesized and characterized some N-phenylcarbazoles with different substituents on the phenyl group. Based on a comparative study, the possible electropolymerization mechanisms of the NO2-3Cz and NH2-3Cz monomers are suggested; that of the former is through carbazole–carbazole coupling, and the latter is through both carbazole–carbazole and NH2–carbazole coupling.

Two series of novel diamide- or diimide-cored N-phenylcarbazole dendrons were synthesized from condensation reactions of 3,6-di(carbazol-9-yl)-N-(4-aminophenyl)carbazole (NH2-3Cz) with aromatic dicarboxylic acids and tetracarboxylic dianhydrides, respectively. These dendrons can be electropolymerized into crosslinked poly(amide-carbazole) and poly(imide-carbazole) films on the electrode surface in an electrolyte solution via the coupling reactions between carbazole radical cations. Cyclic voltammograms of the electro-generated polymer films showed two reversible oxidation redox couples accompanied by a color change from the colorless neutral state to the yellow-green and blue oxidized forms in the range of 1.11–1.34 V. The electrochromic behavior of the film is clearly interpreted on the basis of spectroelectrochemical studies. Single layer electrochromic cells were also fabricated as preliminary evaluation for their application as electrochromic devices.

A carbazolyl-substituted triphenylamine derivative, 4-(N-carbazolyl)triphenylamine (TPACz), was synthesized and used to build a fluorescent and electrochromic polymeric film (PTPACz) on the ITO-glass surface by electrochemical oxidative coupling reactions. The electrodeposited PTPACz film showed blue emission (λmax = 424 nm) and exhibited reversible electrochemical redox processes and stable color changes upon electro-oxidation, which can be switched by potential modulation. The remarkable electrochromic behavior of the film is clearly interpreted on the basis of spectroelectrochemical studies. A dimethoxy-substituted derivative of TPACz, namely 4,4′-dimethoxy-4′′-(N-carbazolyl)triphenylamine (MeOTPACz), was also synthesized and characterized for a comparative study. Repetitive cyclic voltammetry scanning of MeOTPACz in an electrolyte/acetonitrile solution resulted in an electroactive dimeric film of (MeOTPACz)2 on the electrode surface. Electrochromic devices using PTPACz or (MeOTPACz)2 as an active layer were also fabricated as preliminary investigations for electrochromic applications.

This work deals with the synthesis and characterization of a new m-phenylenediamine-type monomer with pendent 3,6-dimethoxycarbazole group, namely N-(4-(3,6-dimethoxycarbazol-9-yl)phenyl)-3,5-diaminobenzamide (2), and its derived aromatic polyamides and polyimides. New electroactive aromatic polyamides were synthesized from diamine 2 with four aromatic dicarboxylic acids via the phosphorylation polyamidation technique, and the polyimides were prepared from equimolar mixtures of 4,4′-oxydianiline and diamine 2 with four aromatic tetracarboxylic dianhydrides via a conventional two-step procedure. All the polyamides and the 6FDA-derived polyimide were readily soluble in many organic solvents and could afford strong and flexible films by solution casting. The polymers showed useful levels of thermal stability with glass-transition temperatures (Tgs) in the range of 237–313 °C and 10% weight-loss temperatures in excess of 450 °C. All the polyamides and polyimides showed reversible electrochemical oxidation, accompanied by strong color changes. By incorporation of electron-donating methoxy groups on the electrochemically active C-3 and C-6 sites of the carbazole unit, the polymers exhibit greatly enhanced electrochemical stability and electrochromic performance in comparison with the analogs without any substituents on the carbazole unit.

Two carbazole end-capped monomers containing triphenylamine or N -phenylcarbazole as an interior core, namely 4,4′-di(carbazol-9-yl)-4″-methoxytriphenylamine (TPA-2Cz) and 3,6-di(carbazol-9-yl)- N -(4-methoxyphenyl)carbazole (PhCz-2Cz), were prepared by a well-known chemistry from readily available reagents. The electrochemistry and electropolymerization of these two monomers were investigated and compared with those of structurally similar analogs with tert -butyl groups attaching on the active sites of the end-capped carbazole units. The polymeric films were built onto ITO/glass surface by repetitive cyclic voltammetry (CV) scanning of the monomer solutions containing an electrolyte. The electro-generated polycarbazole films exhibited high redox-activity and strong color changes upon electro-oxidation, which can be switched by potential modulation. The remarkable electrochromic behavior of the film was clearly interpreted on the basis of spectroelectrochemical studies, and the electrochromic stability was evaluated by the electrochromic switching studies.

Two series of new triptycene-containing poly(ester-amide)s and poly(ester-imide)s were prepared from 1,4-bis(3-aminobenzoyloxy)triptycene with various aromatic dicarboxylic acids and dianhydrides, respectively. The synthesis of the poly(ester-amide)s was achieved by the phosphorylation polyamidation reaction by means of triphenyl phosphite and pyridine, and the synthesis of the poly(ester-imide)s included ring-opening polyaddition to give poly(amic acid)s followed by thermal imidization and chemical imidization to polyimides. All the poly(ester-amide)s and most of the poly(ester-imide)s presented good solubility in many organic solvents and could be solution-cast into transparent and flexible films. These poly(ester-amide)s and poly(ester-imide)s displayed discernible glass-transition temperatures (Tgs) between 242 and 298 °C in the DSC traces and showed moderate thermal stability with 10 wt% loss temperatures above 464 °C in nitrogen or air. These highly optically transparent polymer films possess an ultraviolet-visible absorption cut-off wavelength (λ0) down to 344 nm. 1,4-Bis(4-aminobenzoyloxy)triptycene was also synthesized and used for polymer synthesis; however, less favorable results were obtained.

Two electropolymerizable monomers with a methoxytriphenylamine core linked via amide groups to two triphenylamine (TPA) or N-phenylcarbazole (NPC) terminal groups, namely 4,4′-bis(4-diphenylaminobenzamido)-4′′-methoxytriphenylamine (MeOTPA-(TPA)2) and 4,4′-bis(4-(carbazol-9-yl)benzamido)-4′′-methoxytriphenylamine (MeOTPA-(NPC)2), were synthesized and characterized by FTIR and 1H NMR spectroscopy, mass spectrometry, and cyclic voltammetry. The electrochemical polymerization reactions of these MeOTPA-cored monomers over indium tin oxide (ITO) electrode allow the generation of electroactive poly(amide-amine) films. The electro-generated polymer films exhibited reversible redox processes and multi-colored electrochromic behaviors upon electro-oxidation, together with moderate coloration efficiency and cycling stability. The optical density changes (ΔOD) were observed in the range of 0.18–0.68 at specific absorption maxima, with the calculated coloration efficiencies of 42–123 cm2/C. Single-layer electrochromic devices using the electrodeposited polymer films as active layers were fabricated for the preliminary investigation of their electrochromic applications.

A novel class of fluorinated poly(ether-imide)s (PEIs) with anthraquinone (AQ) units were prepared from the polycondensation reactions of a newly synthesized AQ-dietheramine monomer, namely 2,6-bis(4-amino-2-trifluoromethylphenoxy)-anthraquinone, with aromatic tetracarboxylic dianhydrides via a conventional two-step technique. The fluorinated polyimides exhibited enhanced solubility and optical transparency because of increased free volume caused by the CF 3 substituents. Furthermore, the PEIs showed high thermal stability, with glass-transition temperatures of 263–312 °C and decomposition temperatures in excess of 500 °C. These PEIs were also investigated by cyclic voltammetry and spectroelectrochemistry. Preliminary results reveal that these AQ-based PEIs are potentially useful as cathodically coloring red electrochromes.

We developed a new efficient procedure for the synthesis of a bistriphenylamine diamine monomer, N,N′-bis(4-aminophenyl)-N,N′-bis(4-methoxyphenyl)-1,4-phenylenediamine (3). A new dicarboxylic acid monomer bearing two built-in imide rings, namely N,N′-bis(trimellitimidophenyl)-N,N′-bis(4-methoxyphenyl)-1,4-phenylenediamine (4), was synthesized from the condensation of diamine 3 with two equivalent amounts of trimellitic anhydride. Several novel electroactive poly(amide-imide)s (PAIs) containing N,N′-di(4-methoxyphenyl)-N,N′-diphenyl-p-phenylenediamine [TPPA(OMe)2] units have been prepared by the phosphorylation polyamidation reactions from diamine 3 with four imide ring-preformed dicarboxylic acids or from diimide-diacid 4 with 4,4′-oxydianiline and diamine 3, respectively. All the PAIs were readily soluble in many organic solvents and could be solution-cast into tough and flexible polymer films. These PAIs exhibited glass-transition temperatures (Tgs) in the range 206–292 °C, and most of them did not show significant weight-loss before 450 °C. The PAI films revealed reversible electrochemical oxidation processes accompanied with strong color changes from the pale yellow neutral state to yellowish green and deep blue oxidized. Incorporating the TPPA(OMe)2 unit on the amide side of PAIs led to lower oxidation potentials and higher redox and electrochromic stability.

Four bis(amide-triarylamine) derivatives featuring a triptycene as an interior core and terminal electroactive triphenylamine (TPA) or N-phenylcarbazole (NPC) groups were prepared by the condensation reactions from 1,4-bis(4-aminophenoxy)triptycene with 4-carboxytriphenylamine and N-(4-carboxyphenyl)carbazole, respectively, and from 1,4-bis(4-carboxyphenoxy)triptycene with 4-aminotriphenylamine and N-(4-aminophenyl)carbazole, respectively. The electrochemistry and electropolymerization of these bis(amide-triarylamine) derivatives were investigated. The stability of the oxidized forms of the bis(amide-triarylamine)s is affected by the orientation of amide linkage and the structure of terminal triarylamine unit. Two of the bis(amide-triarylamine)s could be electropolymerized into robust films on the electrode surface in an electrolyte solution. The electrogenerated polymer films exhibited reversible electrochemical oxidation processes and strong color changes upon electro-oxidation, which can be switched by potential modulation. The electrochromic properties of the films were evaluated by the spectroelectrochemical and electrochromic switching studies. The TPA-based film showed better electrochromic performance than the NPC-based one.

A series of novel aromatic polyimides were synthesized from N,N-di(4-aminophenyl)-N′,N′-diphenyl-4,4′-oxydianiline and aromatic tetracarboxylic dianhydrides through a conventional two-step procedure. Most of the polyimides exhibited reasonable solubility in organic solvents and could afford robust films via solution casting. The polyimides exhibited high thermal stability, with glass transition temperatures in the range 227–273 °C and 10% weight-loss temperatures in excess of 550 °C. All the polyimide films showed ambipolar redox and multi-electrochromic behaviors. They exhibited two reversible oxidation redox couples at 0.94–0.98 and 1.09–1.12 V versus Ag/AgCl in acetonitrile solution. A coupling reaction between the radical cations of the pendent triphenylamine units occurred during the oxidative process forming a tetraphenylbenzidine structure which resulted in an additional redox state and color change. © 2014 Society of Chemical Industry

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 (Td) at a 10% weight-loss in nitrogen and air were recorded at 556–568 °C and 537–555 °C, respectively. The glass-transition temperatures (Tg) 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

A series of new fluorinated aromatic poly(ether imide)s (PEIs) were prepared from highly contorted 2,2′-bis(3,4-dicarboxyphenoxy)biphenyl dianhydride and various trifluoromethyl-containing bis(ether amine)s via chemical or thermal imidization. All the PEIs showed good solubility in a variety of organic solvents and could afford flexible, colorless, and transparent thin films via solution-casting. They showed cut-off wavelengths of Uv-vis absorptions below 380 nm and very low yellowness index (b*

A series of aromatic polyimides with pendent triphenylamine group were synthesized from equimolar mixtures of 4,4′-oxydianiline (ODA) and 4-(3,5-diaminobenzamido)triphenylamine ( 4 ), 4-(3,5-diaminobenzamido)-4′,4″-di- tert -butyltriphenylamine ( t -Bu - 4 ) or 4-(3,5-diaminobenzamido)-4′,4″-dimethoxytriphenylamine ( MeO-4 ) with two aromatic tetracarboxylic dianhydrides (DSDA or 6FDA) via a conventional two-step procedure that included a ring-opening polyaddition to give poly(amic acid)s, followed by chemical imidization. These polyimides exhibited good solubility in polar organic solvents and could be solution-cast into flexible and strong films. They showed excellent thermal stability, with T g values in the range of 284–309 °C. The polyimides derived from diamines t -Bu - 4 and MeO-4 exhibited reversible electrochemical oxidation, accompanied by strong color changes with high contrast ratio and electrochromic stability. For the polyimides derived from diamine 4 , the coupling reaction between the triphenylamine radical cations occurred during the oxidative process forming a tetraphenylbenzidine structure, which resulted in an additional oxidation state and color change together with enhanced near-IR absorption at fully oxidized state.