Thieno[3,2‐b]Thiophene End‐Capped all‐Sulfur Analog of 3,4‐Ethylenedioxythiophene and its Eletrosynthesized Polymer: Is Distorted Conformation Not Suitable for Electrochromism?

By employing planar thieno[3,2‐b]thiophene (TT) as end‐capped units and famous 3,4‐ethylenedioxythiophene (EDOT) or its all‐sulfur analog 3,4‐ethylenedithiathiophene (EDTT) as cores, two conjugated oligomer, TT‐EDOT‐TT and TT‐EDTT‐TT, have been synthesized and electropolymerized into electrochromic polymer films, P(TT‐EDOT‐TT) and P(TT‐EDTT‐TT), respectively. Due to strongly noncovalent inter/intramolecular interactions from S? S attraction of TT‐EDTT‐TT, it has twisted molecular configuration in contrast to planar TT‐EDOT‐TT. Spectroscopic, electrochemical, morphological as well as theoretical calculation studies of these oligomers or polymers were carried out to reveal the significant influence of such molecular geometry on their physicochemical and optoelectronic properties. According to electrochromic kinetics, P(TT‐EDTT‐TT) presented preferable electrochromic behavior such as the higher optical contrast (70.8%), favorable coloration efficiency (331.3 cm² C^?1) and fast response time (0.72 s). This research will help us deeply understand the effect of spatial organization of precursor molecules on the properties of electrochromic polymers and provides a promising strategy to develop high‐performance electrochromic materials. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 1041–1048     

Low band‐gap diketopyrrolopyrrole‐containing polymers for near infrared electrochromic and photovoltaic applications

Donor–acceptor type polymers bearing diketopyrrolopyrrole and 3,4‐ethylenedioxythiophene units are reported. The polymers are green and exhibit very low band‐gaps (1.19 eV) with strong and broad absorption (maxima of about 830 nm) in the near infrared (NIR) region in their neutral film states. The polymers display color changes between dark green and light blue with exceptional optical contrasts in the NIR regions of up to 78 and 63% as thin films and single‐layer electrochromic devices, respectively. Fast switching, good stabilities as well as high coloration efficiencies (743–901 cm² C^?1) were also observed. The polymers could also be potentially used as photovoltaic material, with a power conversion efficiency of up to 1.68%. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1287–1295     

Multifunctional triphenylamine polymers synthesized via direct (hetero) arylation polymerization

The design rules for creating multifunctional organic electronic materials are currently limited. By copolymerizing twisted triphenylamine (TPA) and electron rich dioxythiophene (XDOT) monomers via Direct (Hetero) Arylation Polymerization (DHAP), a set of polymers are obtained that perform as yellow to transmissive electrochromic (EC) films with up to 45% contrast, as well as in electroluminescent (EL) applications, achieving a luminance of ∼450 cd/m² in yellow‐green polymer light‐emitting diodes (PLEDs). In addition, polymerizing TPA with a donor‐acceptor‐donor monomer results in a low‐bandgap polymer that achieves power conversion efficiencies up to 2.5% when blended with PC₇₁BM in conventional organic photovoltaic (OPV) devices. Incorporation of TPA units into the polymer backbone largely breaks any aggregation and ordering in the solid‐state, leading to highly soluble materials that form smooth, reproducible thin films. The TPA unit also serves to break conjugation throughout the polymer backbone, providing precise control over optical and electronic properties through choice of comonomer. These results suggest that TPA copolymers can be useful for achieving multi‐functionality without sacrificing facile solution processability, making them promising candidates for multifunctional devices like dual EC/EL displays. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 147–153     

Synthesis and optical properties of novel blue‐light‐emitting poly(p‐phenylene vinylene) derivatives with pendant oxadiazole or cyano groups

Two novel poly(p‐phenylene vinylene) polymers, which carried side substituents with cyano groups or 1,3,4‐oxadiazole, were synthesized by Heck coupling. They consisted of alternating conjugated segments and nonconjugated aliphatic spacers. The polymers had moderate molecular weights, were amorphous, and dissolved readily in tetrahydrofuran and halogenated organic solvents. They were stable up to approximately 340 °C in N₂ and 290 °C in air, and the anaerobic char yield was around 60% at 800 °C. The polymer with cyano side groups emitted blue light in solutions and thin films with identical photoluminescence (PL) maximum at 450 nm; this supported the idea that chain interactions were hindered even in the solid state. The PL maximum of this polymer in thin films was blueshifted upon annealing at 120 °C, indicating a thermochromic effect as a result of conformational changes in the polymer backbone. The polymer containing side substituents with oxadiazole rings emitted blue light in solutions with a PL maximum at 474 nm and blue‐greenish light in thin films with a PL maximum at 511 nm. The PL quantum yields of the polymers in tetrahydrofuran were 0.13–0.24. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1768–1778, 2004     

A new high‐performance blue to transmissive electrochromic material and use of silver nanowire network electrodes as substrates

Synthesis of a novel, high‐performance blue to transmissive switching electrochromic material is described. The polymer (P1) was prepared by both electrochemical ( P1E ) and chemical ( P1C ) means from the corresponding monomer. The electrochemically synthesized polymer ( P1E ) revealed 64% optical contrast change (on ITO) in the visible region and very fast switching times of 0.32 s (coloration) and 0.90 s (bleaching). On the other hand, the chemically synthesized, solution processable polymer ( P1C ) also showed a high optical contrast value (49%, on ITO) with very fast switching times of 0.86 s for coloration and 0.57 s for bleaching. These high optical contrast values coupled with fast switching times place these materials along with high‐performance blue to transmissive electrochromic polymers. Significantly, these improved characteristics were achieved by side chain engineering of a known, inferior blue to transmissive polymer, PBEBT. Towards fabrication of flexible electrochromic devices, the performance of P1C was also tested on silver nanowire network electrodes. Even though the full potential of the material could not be demonstrated, a good optical contrast of 24% was achieved using these electrodes. Under the same potential range allowed by silver nanowire network electrodes, P1C on ITO showed an optical contrast of 30%. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 1680–1686     

Conjugated copolymers comprised cyanophenyl‐substituted spirobifluorene and tricarbazole‐triphenylamine repeat units for blue‐light‐emitting diodes

A series of conjugated blue‐light‐emitting copolymers, PTC‐1 , PTC‐2 , and PTC‐3, comprised different ratios of electron‐withdrawing segments (spirobifluorene substituted with cyanophenyl groups) and electron‐donating segments (tricarbazole‐triphenylamines), has been synthesized. The structures of these polymers were characterized and their thermal, photophysical, electrochemical, and electroluminescence properties were measured. Incorporation of rigid spirobifluorene units into the copolymers led to blue‐shifted absorption peaks in dilute toluene solution. Cyclic voltammetric measurement indicated the bandgaps of the polymers were in the range of 2.77–2.94 eV. It was found that increasing cyanophenyl‐spirobifluorene content in the polymer backbone lowered both the HOMO and LUMO energy levels of the copolymers, which was beneficial for electron injection/transporting in the polymer layer of the device. OLED device evaluation indicated that all the polymers emitted sky blue to deep blue light when the pure polymers were used as the emissive layers in the devices with a configuration of ITO/PEDOT:PSS/polymers/CsF/Ca/Al. The devices have been optimized by doping 30 wt % PBD into the polymer layers. Among the doped devices, PTC‐2 showed the best performance with the turn‐on voltage of 3.0 V, maximum brightness of 7257 cd/m², maximum current efficiency of 1.76 cd/A, and CIE coordinates of (0.15, 0.14). © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 292–301, 2010     

Poly[2,7‐(9,9‐dihexylfluorene)‐alt‐pyridine] with donor‐acceptor architectures: A new series of blue‐light‐emitting alternating copolymers

A novel series of well‐defined alternating poly[2,7‐(9,9‐dihexylfluorenyl)‐alt‐pyridinyl] (PDHFP) with donor‐acceptor repeat units were synthesized using palladium (0)‐catalyzed Suzuki cross‐coupling reactions in good to high yields. In this series of alternating polymers, 2, 7‐(9,9‐dihexylfluorenyl) was used as the light emitting unit, and the electron deficient pyridinyl unit was employed to provide improved electron transportation. These polymers were characterized by ¹H‐NMR and ¹³C‐NMR, gel permeation chromatography (GPC), thermal analyses, and UV‐vis and fluorescence spectroscopy. The glass transition temperature of copolymers in nitrogen ranged from 110 to 148 °C, and the copolymers showed high thermal stabilities with high decomposition temperatures in the range of 350 to 390 °C in air. The difference in linkage position of pyridinyl unit in the polymer backbone has significant effects on the electronic and optical properties of polymers in solution and in film phases. Meta‐linkage (3,5‐ and 2,6‐linkage) of pyridinyl units in the polymer backbone is more favorable to polymer for pure blue emission and prevention of aggregation of polymer chain than para‐linkage (2,5‐linkage) of the pyridinyl units. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4792–4801, 2004     

Highly efficient and stable blue‐light‐emitting binaphthol‐fluorene copolymers: A joint experimental and theoretical study of the main‐chain chirality

In a quest for the main‐chain chiral and highly stable blue‐light‐emitting π‐conjugated polymers, a novel series of soluble conjugated random and alternating copolymers (PF‐BN) derived from fluorene and axially chiral 1,1′‐binaphthol (BINOL) were successfully synthesized by Suzuki coupling polymerization. The polymer structures, optical properties, and their electrochemical properties were investigated by ¹H NMR, TGA/DSC, UV‐Vis absorption, photoluminescence, cyclic voltammetry, circular dichroism spectroscopy, and DFT calculations. The blue‐light‐emitting BINOL‐containing copolymers with proper content of BINOL show highly efficient photoluminescence and ultra highly stable light‐emission with almost unchanged fluorescent spectra after annealing at 200 °C in air for 10 h. The joint experimental and theoretical study of the main‐chain chirality reveals that (1) the chirality of BINOL can be transferred to the polymer backbone, (2) the effective conjugation length is about one BINOL and three fluorenes, (3) the main active chiral block in the copolymers is probably composed by one BINOL with the other two or three fluorenes, and (4) the dihedral angle in the PF‐BN copolymers should be larger than 105°. The incorporation of BINOL into the polyfluorene backbone is an effective way to produce highly efficient and stable blue‐light‐emitting main‐chain chiral conjugated polymer with interesting optoelectronic properties. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3868–3879, 2010     

Synthesis and electrochromism of novel organosoluble polyarylates bearing triphenylamine moieties

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

Synthesis and characterization of new blue‐light‐emitting polymers based on PPP and PPV having fluorene pendant at vinyl bridge

The new poly(arylene vinylene) derivatives, which are composed of biphenylene vinylene phenylene vinylene, biphenylene vinylene m‐phenylene vinylene, terphenylene vinylene phenylene vinylene, and terphenylene vinylene m‐phenylene vinylene as backbone and bulky fluorene pendants at each vinyl bridge, were designed, synthesized, and characterized. The obtained polymers showed weight‐average molecular weights of 11,100–39,800 with polydispersity indexes ranging from 1.5 to 2.1. The resulting polymers were amorphous with high thermal stability and readily soluble in common organic solvents. The obtained polymers showed blue emission (λ_max = 456–475 nm) in PL spectra, and polymer 4 containing terphenylene vinylene m‐phenylene vinylene showed the most blue shifted blue emission (λ_max = 456 nm). The double layer light‐emitting diode devices fabricated by using obtained polymers as emitter emitted bright blue light. The device showed turn on voltage around 6.5 V and brightness of 70–250 cd/m². © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4923–4931, 2006     

Thiophene π bridge effect on bulky side‐chained benzodithiophene‐based photovoltaic polymers

Recently, we have used terthiophene side chain to modify benzo[1,2‐b:4,5‐b′]dithiophene (BDT) to form novel building block for BDT polymers. In this paper, this building block is used to copolymerized with thieno[3,4‐c]pyrrole‐4,6‐dione (TPD) and thieno[3,4‐b]thiophene (TT). This building block and TPD‐ or TT‐based polymers (P1 and P3) show high open circuit voltage (V_OC) (ca. 0.9–0.95 V) and low energy loss (E_g–eV_OC) in solar cells devices compared with similar polymers without bulky side chain. We further introduce thiophene π bridge into these polymers backbone to form two other polymers (P2 and P4). We find this thiophene π bridge does contribute to this bulky side chained benzodithiophene polymer photovoltaic performances, especially for power conversion efficiencies (PCEs). The polymer solar cells (PSCs) performances are moderate in this article due to the serious aggregation in the PSCs active layer. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1615–1622     

Electrochemical synthesis and investigation of poly(1,4-bis(2-(3,4-ethylenedioxy)thienyl)benzene) and its application in an electrochromic device

1,4-Bis(2-(3,4-ethylenedioxy)thienyl)benzene, prepared by Stille cross-coupling reaction was successfully electrochemically polymerized to give polymer 1,4-bis(2-(3,4-ethylenedioxy)thienyl)benzene (PEBE). Characterizations of the resulting polymer PEBE were performed by cyclic voltammetry (CV), UV–vis, Fourier transform infrared spectroscopy and scanning electron microscopy. Moreover, the spectroelectrochemical and electrochromic properties of the polymer film were investigated. The resulting polymer film has distinct electrochromic properties and shows three different colors (deep red, gray, and light blue) under various potentials. At the dedoped state of the polymer, the π–π* transition absorption peak is located at 510?nm and the optical band gap (E _g) was calculated as 1.92?eV. The PEBE film shows a maximum optical contrast (ΔT%) of 31.0?% at 500?nm with a response time of 0.85?s. The coloration efficiency of PEBE film was calculated to be 182.2?cm²C^?1. An electrochromic device (ECD) based on PEBE and poly(3,4-ethylenedioxythiophene) was also constructed and characterized. The response time was measured as 0.4?s, and the coloration efficiency of the device was calculated to be 225.4?cm²C^?1. Furthermore, this ECD exhibited satisfactory optical memories and redox stability.     

A new near‐infrared switchable electrochromic polymer and its device application

A new near‐infrared switchable electrochromic polymer containing carbazole pendant (poly‐SNSC), synthesized by electrochemical polymerization of 2,5‐bis‐dithienyl‐1H‐pyrrole (SNS) main chain, has been prepared. The electrochemical and optical properties of SNSC monomer and its polymer have been investigated. Because of having two different electro‐donor moieties; that is, carbazole and SNS, SNSC gave two separate electrochemical oxidation and also light brown color of the film in the neutral state turn into gray on oxidation. An electrochromic device, contructed in the sandwich configuration [indium tin oxide (ITO)‐coated glass/anodically coloring polymer (poly‐SNSC)//gel electrolyte//cathodically coloring polymer (PEDOT)/ITO‐coated glass] and exhibited a high coloration efficiency (1216 cm² C^–1), a very short response time (about 0.3 s), low driving voltage, and a high redox stability. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Highly stable electrochromic polyamides based on N,N‐bis(4‐aminophenyl)‐N′,N′‐bis(4‐tert‐butylphenyl)‐1,4‐phenylenediamine

A new triphenylamine‐containing aromatic diamine monomer, N,N‐bis(4‐aminophenyl)‐N′,N′‐bis(4‐tert‐butylphenyl)‐1,4‐phenylenediamine, was synthesized by an established synthetic procedure from readily available reagents. A novel family of electroactive polyamides with di‐tert‐butyl‐substituted N,N,N′,N′‐tetraphenyl‐1,4‐phenylenediamine units were prepared via the phosphorylation polyamidation reactions of the newly synthesized diamine monomer with various aromatic or aliphatic dicarboxylic acids. All the polymers were amorphous with good solubility in many organic solvents, such as N‐methyl‐2‐pyrrolidinone (NMP) and N,N‐dimethylacetamide, and could be solution‐cast into tough and flexible polymer films. The polyamides derived from aromatic dicarboxylic acids had useful levels of thermal stability, with glass‐transition temperatures of 269–296 °C, 10% weight‐loss temperatures in excess of 544 °C, and char yields at 800 °C in nitrogen higher than 62%. The dilute solutions of these polyamides in NMP exhibited strong absorption bands centered at 316–342 nm and photoluminescence maxima around 362–465 nm in the violet‐blue region. The polyamides derived from aliphatic dicarboxylic acids were optically transparent in the visible region and fluoresced with a higher quantum yield compared with those derived from aromatic dicarboxylic acids. The hole‐transporting and electrochromic properties were examined by electrochemical and spectro‐electrochemical methods. Cyclic voltammograms of the polyamide films cast onto an indium‐tin oxide‐coated glass substrate exhibited two reversible oxidation redox couples at 0.57–0.60 V and 0.95–0.98 V versus Ag/AgCl in acetonitrile solution. The polyamide films revealed excellent elcterochemical and electrochromic stability, with a color change from a colorless or pale yellowish neutral form to green and blue oxidized forms at applied potentials ranging from 0.0 to 1.2 V. These anodically coloring polymeric materials showed interesting electrochromic properties, such as high coloration efficiency (CE = 216 cm²/C for the green coloring) and high contrast ratio of optical transmittance change (ΔT%) up to 64% at 424 nm and 59% at 983 nm for the green coloration, and 90% at 778 nm for the blue coloration. The electroactivity of the polymer remains intact even after cycling 500 times between its neutral and fully oxidized states. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2330–2343, 2009     

Synthesis and characterization of naphthyl‐substituted poly(p‐phenylenevinylene)s with few structural defects for polymer light‐emitting diodes

A series of naphthyl‐substituted poly(p‐phenylenevinylene)s (2N‐PPV, 4N‐PPV, and NAP‐PPV) has been synthesized and characterized by Fourier transform IR, ¹H NMR, and elemental analysis. The polymers possess excellent solubility, high molecular weights, good thermal stability, and high photoluminescence efficiencies. Thermogravimetric analysis reveals the onset of degradation to be 347, 301, and 306 °C for 2N‐PPV, 4N‐PPV, and NAP‐PPV, respectively. The differential scanning calorimetry investigation gives the respective glass‐transition temperature values of 118, 135, and 141 °C. The UV and photoluminescence spectra measurements reveal that the polymers exhibit similar optical properties, indicating that side‐chain substitution has little effect on the optical properties of this series of polymers. Proton NMR measurement of the signal due to tolane–bisbenzyl defects at around 2.7 ppm indicates that all the polymers have negligible amounts of tolane–bisbenzyl defects along the polymer main chain as a result of the steric bulk imposed by the naphthalene side chain. The highest occupied and lowest unoccupied molecular orbital energy levels of the polymers are investigated through cyclic voltammetry. Polymer light‐emitting diodes utilizing the polymers as the emissive layer with a configuration of indium tin oxide/poly(3,4‐ethylenedioxythiophene)/polymer/Ba/Al are fabricated and evaluated. The diodes emit blue‐green to yellow‐green light with maximum peaks at 518, 542, and 486 nm for 2N‐PPV, 4N‐PPV, and NAP‐PPV, respectively. The respective turn‐on electric fields of the diodes are 0.84, 0.69, and 0.83 MV/cm and the respective maximum external quantum efficiencies are 0.08, 0.54, and 0.02%. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1647–1657, 2004     

A new donor‐acceptor type polymeric material from a thiophene derivative and its electrochromic properties

A new electrochromic polymer, poly(2,3,5,8‐tetra(thiophen‐2‐yl)quinoxaline) (PTTQ), was synthesized electrochemically and its electrochromic properties were investigated. The polymer was characterized by Cyclic Voltammetry, Fourier Transform infrared spectroscopy, UV‐Vis‐NIR Spectroscopy, and colorimetry. Spectroelectrochemistry analysis demonstrated that the polymer can undergo both p‐ and true n‐type doping processes. The polymer, (PTTQ), has three accessible color states: an oxidized transmissive, a neutral light bluish‐green, and a reduced transmissive light gray. Switching ability of the polymer was evaluated by kinetic studies. The polymer revealed an excellent optical contrast of 98% in the NIR region. Outstanding optical contrast in the NIR region, high stability and fast switching times make this polymer an excellent candidate for NIR device applications. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3723–3731, 2008     

Red,green, and blue electrochromism in ambipolar poly(amine–amide–imide)s based on electroactive tetraphenyl‐p‐phenylenediamine units

A series of novel poly(amine–amide–imide)s (PAAIs) based on tetraphenyl‐p‐phenylenediamine (TPPA) units showing anodically/cathodically electrochromic characteristic with three primary colors [red, green, and blue (RGB)] were prepared from the direct polycondensation of the TPPA‐based diamine monomer with various aromatic bis(trimellitimide)s. These multicolored electrochromic polymers were readily soluble in polar organic solvents and showed excellent thermal stability associated with high glass‐transition temperatures (288–314 °C) and high‐char yield (higher than 60% at 800 °C in nitrogen). The PAAI films revealed electrochemical oxidation and reduction accompanied with high contrast of optical transmittance color changes from the pale yellow neutral state to the green/blue oxidized state and red reduced state, respectively. The electrochromic films had high‐coloration efficiency (CE = 178 and 242 cm²/C at the first and the second stages, respectively), low‐switching time, and good redox stability, which still retained a high electroactivity after long‐term redox cycles. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

A newly-designed self-powered electrochromic window

By converting incident light into electric power, self-powered electrochromic window (SP-ECW) can achieve color change in electrochromic layer with no need for external voltage. In this work, a newly-designed SP-ECW is proposed for altering its color between deep blue and colorless state according to on/off state of incident light. The device consists of a working electrode with planar integration of photovoltaic (PV) and electrochromic (EC) elements on one electrode, a platinum counter electrode and a redox electrolyte comprising Br^–/Br ₃ ^– couple. A high transmittance modulation of 41% at 582 nm is obtained. Electrical energy converted from light is not only sufficient to drive the device, but also can be outputted to the external circuit.     

多色显示树枝状聚(3, 6-双噻吩咔唑)及其共聚物的电化学和电致变色性能

设计合成了一种新型的基于咔唑单元的树枝状3, 6-双噻吩咔唑衍生物(BTCPh),通过电化学聚合法制备出其均聚物及与3, 4-乙烯二氧噻吩(EDOT)的共聚物薄膜.利用电化学工作站-紫外可见光谱联用装置对两种聚合物的光谱电化学和电致变色(EC)性能进行表征.测试结果表明,均聚物(PBTCPh)薄膜在不同电压下可显示黄、绿、蓝、灰四种颜色;而EDOT单元的引入使共聚物P(BTCPh-EDOT)进一步增加了掺杂态,从而显示出更加丰富的五种颜色(橙、绿、棕绿、蓝、灰).此外,两种聚合物薄膜均具有良好的光学对比度和快速的响应速度,因而使其在智能窗及显示器方面展现了潜在的应用前景.     

New polyimides incorporated with diphenylpyrenylamine unit as fluorophore and redox‐chromophore

A series of novel polyimides based on N,N‐di(4‐aminophenyl)‐1‐aminopyrene and aromatic or alicyclic tetracarboxylic dianhydrides were synthesized. The polymers exhibited good solubility in many polar organic solvents and could afford robust films via solution casting. The polyimides derived from aromatic dianhydrides exhibited high thermal stability and high glass‐transition temperatures (333–364 °C). Cyclic voltammetry studies of the polymer films showed that these polyimides are both p and n dopable and have multicolored electrochromic states. For the polyimides derived from alicyclic dianhydrides, they revealed a strong blue‐light emission with high fluorescence quantum yields (?_PL > 45%) and a marked solvatochromic behavior. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011