Synthesis and characterization of alt‐bipyridinylene‐phenylene copolymers containing ruthenium(II) complexes

Poly{bis(4,4′‐tert‐butyl‐2,2′‐bipyridine)–(2,2′‐bipyridine‐5,5′‐diyl‐[1,4‐phenylene])–ruthenium(II)bishexafluorophosphate} ( 3a ), poly{bis(4,4′‐tert‐butyl‐2,2′‐bipyridine)–(2,2′‐bipyridine‐4,4′‐diyl‐[1,4‐phenylene])–ruthenium(II)bishexafluorophosphate} ( 3b ), and poly{bis(2,2′‐bipyridine)–(2,2′‐bipyridine‐5,5′‐diyl‐[1,4‐phenylene])–ruthenium(II)bishexafluorophosphate} ( 3c ) were synthesized by the Suzuki coupling reaction. The alternating structure of the copolymers was confirmed by ¹H and ¹³C NMR and elemental analysis. The polymers showed, by ultraviolet–visible, the π–π* absorption of the polymer backbone (320–380 nm) and at a lower energy attributed to the d–π* metal‐to‐ligand charge‐transfer absorption (450 nm for linear 3a and 480 nm for angular 3b ). The polymers were characterized by a monomodal molecular weight distribution. The degree of polymerization was approximately 8 for polymer 3b and 28 for polymer 3d . © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2911–2919, 2004     

New liquid‐crystal alignment agents based on fluorinated polyimides with trifluoromethyl‐substituted benzene or diphenylether in the side chain

Fluorinated copolyimides derived from 4,4′‐oxydiphthalic anhydride (ODPA) with 4,4′‐oxydianline (ODA) and trifluoromethyl‐containing aromatic diamines have been synthesized and characterized. The trifluoromethyl‐containing diamines include 2,4‐diamino‐3′‐trifluoromethylazobenzene, 2,4‐diamino‐1‐[(4′‐trifluoromethylphenoxy) phenyl] aniline, 3,5‐diamino‐1‐[(4′‐trifluoromethylphenoxy) phenyl] benzamide, 3,5‐diamino‐1‐[(3′‐trifluoromethyl) phenyl] benzamide, 1,4‐bis(4′‐aminophenoxy)‐2‐(3′‐trifluoromethylphenyl) benzene, 3,5‐diaminobenzenetrifluoride, 4,4′‐diamino‐4″‐(p‐trifluoromethyl phenoxy) triphenylamine, and 4‐[(4′‐trifluoromethylphenoxy) phenyl]‐2,6‐bis(4″‐aminophenyl)pyridine. Strong and flexible copolyimide films, produced by casting the polyamic acid solution followed by thermal imidization, exhibited great thermal stability and high mechanical properties. The polyimides had an ultraviolet–visible absorption cutoff at 330–340 nm and pretilt angles as high as 20° for nematic liquid crystals, making them great potential candidates for advanced liquid‐crystal display applications. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1583–1593, 2002     

Soluble polyimides containing 1,4:3,6‐dianhydro‐d‐glucidol and fluorinated units: Preparation,characterization, optical,and dielectric properties

Aiming to develop soluble and colorless polyimides, two novel diamines, 2,5‐bis(2‐trifluoromethyl‐4‐amino‐phenoxy)‐1,4:3,6‐dianhydrosorbitol (2a) and 2,5‐bis(2‐methyl‐4‐amino‐phenoxy)‐1,4:3,6‐dianhydrosorbitol (2b), were designed and synthesized by the reduction of corresponding dinitro monomer which was obtained via solvent‐free melt heating method. Polyimides (PI–(1–5)) containing 1,4:3,6‐dianhydro‐d ‐glucidol fragments were prepared from 2a and five kinds of common dianhydrides and PI–6 was synthesized from 2b and 4,4′‐(hexafluoroisopropylidene)‐diphthalic anhydride (6FDA) via a two‐step thermal imidization. All the polyimides were readily soluble in common polar solvents and could afford flexible, tough, and transparent films with transparency as high as 87% at 450 nm. Meanwhile, PI–(1–6) exhibited unexpectedly low dielectric constants of 2.02–2.52 at 1 MHz. In addition, analogs PI–7 derived from 2,5‐bis(4‐amino‐phenoxy)‐1,4:3,6‐dianhydrosorbitol (2c) and 6FDA and PI–8 derived from 4,4′‐bis(4‐amino‐2‐trifluoromethylphenoxy)biphenyl (2d) and 6FDA were also obtained via a two‐step thermal imidization for comparision with PI–(1–6) on aspects of thermal, mechnical, optical, electrical, and morphological properties. The structure–property relationships of PI–(1–8) were discussed in detail. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 3253–3265     

Synthesis and Photovoltaic Properties of Cyclopentadithiophene‐Based Low‐Bandgap Copolymers That Contain Electron‐Withdrawing Thiazole Derivatives

We have synthesized four types of cyclopentadithiophene (CDT)‐based low‐bandgap copolymers, poly[{4,4‐bis(2‐ethylhexyl)‐4H‐cyclopenta[2,1‐b:3,4‐b′]dithiophene‐2,6‐diyl}‐alt‐(2,2′‐bithiazole‐5,5′‐diyl)] ( PehCDT‐BT ), poly[(4,4‐dioctyl‐4H‐cyclopenta[2,1‐b:3,4‐b′]dithiophene‐2,6‐diyl)‐alt‐(2,2′‐bithiazole‐5,5′‐diyl)] ( PocCDT‐BT ), poly[{4,4‐bis(2‐ethylhexyl)‐4H‐cyclopenta[2,1‐b:3,4‐b′]dithiophene‐2,6‐diyl}‐alt‐{2,5‐di(thiophen‐2‐yl)thiazolo[5,4‐d]thiazole‐5,5′‐diyl}] ( PehCDT‐TZ ), and poly[(4,4‐dioctyl‐4H‐cyclopenta[2,1‐b:3,4‐b′]dithiophene‐2,6‐diyl)‐alt‐{2,5‐di(thiophen‐2‐yl)thiazolo[5,4‐d]thiazole‐5,5′‐diyl}] ( PocCDT‐TZ ), for use in photovoltaic applications. The intramolecular charge‐transfer interaction between the electron‐sufficient CDT unit and electron‐deficient bithiazole (BT) or thiazolothiazole (TZ) units in the polymeric backbone induced a low bandgap and broad absorption that covered 300 nm to 700–800 nm. The optical bandgap was measured to be around 1.9 eV for PehCDT‐BT and PocCDT‐BT , and around 1.8 eV for PehCDT‐TZ and PocCDT‐TZ . Gel permeation chromatography showed that number‐average molecular weights ranged from 8000 to 14 000 g mol^?1. Field‐effect mobility measurements showed hole mobility of 10^?6–10^?4 cm² V^?1 s^?1 for the copolymers. The film morphology of the bulk heterojunction mixtures with [6,6]phenyl‐C₆₁‐butyric acid methyl ester (PCBM) was also examined by atomic force microscopy before and after heat treatment. When the polymers were blended with PCBM, PehCDT‐TZ exhibited the best performance with an open circuit voltage of 0.69 V, short‐circuit current of 7.14 mA cm^?2, and power conversion efficiency of 2.23 % under air mass (AM) 1.5 global (1.5 G) illumination conditions (100 mW cm^?2).     

Electrochemical Reduction of 4,4′‐(2,2,2‐Trichloroethane‐1,1‐diyl)‐ bis(chlorobenzene) (DDT) and 4,4′‐(2,2‐Dichloroethane‐1,1‐diyl)‐ bis(chlorobenzene) (DDD) at Carbon Cathodes in Dimethylformamide

In dimethylformamide containing tetramethylammonium tetrafluoroborate, cyclic voltammograms for reduction of 4,4′‐(2,2,2‐trichloroethane‐1,1‐diyl)bis(chlorobenzene) (DDT) at a glassy carbon cathode exhibit five waves, whereas three waves are observed for the reduction of 4,4′‐(2,2‐dichloroethane‐1,1‐diyl)bis(chlorobenzene) (DDD). Bulk electrolyses of DDT and DDD afford 4,4′‐(ethene‐1,1‐diyl)bis(chlorobenzene) (DDNU) as principal product (67–94%), together with 4,4′‐(2‐chloroethene‐1,1‐diyl)bis(chlorobenzene) (DDMU), 1‐chloro‐4‐styrylbenzene, and traces of both 1,1‐diphenylethane and 4,4′‐(ethane‐1,1‐diyl)bis(chlorobenzene) (DDO). For electrolyses of DDT and DDD, the coulometric n values are essentially 4 and 2, respectively. When DDT is reduced in the presence of a large excess of D₂O, the resulting DDNU and DDMU are almost fully deuterated, indicating that reductive cleavage of the carbon–chlorine bonds of DDT is a two‐electron process that involves carbanion intermediates. A mechanistic scheme is proposed to account for the formation of the various products.     

Synthesis and micropatterning properties of a novel base‐soluble,positive‐working,photosensitive polyimide having an o‐nitrobenzyl ether group

A novel positive‐working, photosensitive polyimide, poly[1,4‐phenyleneoxy‐1,4‐phenylene‐2,2′‐di(2‐nitrobenzyloxy)benzophenone‐3,3′,4,4′‐tetracarboxdiimide] (OPI‐Nb), developable with an aqueous base was prepared by the o‐nitrobenzylation of a polyimide, poly(1,4‐phenyleneoxy‐1,4‐phenylene‐2,2′‐dihydroxybenzophenone‐3,3′,4,4′‐tetracarboxdiimide) (OPI), derived from 2,2′‐dihydroxy‐3,3′,4,4′‐benzophenonetetracarboxylic dianhydride (DHBA) and 4,4′‐oxydianiline, and it micropatterning properties were investigated. The o‐nitrobenzylation of OPI to OPI‐Nb was conducted with o‐nitrobenzyl bromide in N‐methyl‐2‐pyrrolidinone containing Et₃N. The DHBA monomer was synthesized by exhaustive KMnO₄ oxidation of bis(2‐dimethoxy‐3,4‐dimethylphenyl)methane obtained by etherification of bis(2‐hydroxy‐3,4‐dimethylphenyl)methane with iodomethane, followed by deprotection of the methoxy groups and cyclodehydration of the obtained 2,2′‐dihydroxy‐3,3′4,4′‐benzophenonetetracarboxylic acid. The intermediate bis(2‐hydroxy‐3,4‐dimethylphenyl)methane was prepared by the condensation of 2,3‐dimethylphenol with paraformaldehyde. The degree of o‐nitrobenzylation was determined to be over 94 mol % from ¹H NMR absorption of benzylic CH₂ protons. The aromatic OPI was perfectly soluble in a dilute aqueous NaOH solution and tetramethylammonium hydroxide (TMAH), whereas OPI‐Nb was not even swellable in them. In the micropatterning process, OPI‐Nb showed a line‐width resolution of 0.4‐μm and a sensitivity of 5.4 J/cm² when its thin films were irradiated with 365‐nm light and developed with a 2.38% aqueous TMAH solution at room temperature for 90 s. The thickness loss of OPI‐Nb films measured after postbaking at 350 °C was in the 8–9% range. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 776–788, 2007     

Synthesis,characterization and solid‐phase extraction properties of novel bis(diazo‐azomethine) ligands supported on mesoporous silica

The novel mesoporous silica‐supported bis(diazo‐azomethine) compounds have been synthesized and characterized successively. In the first step, 1,3‐phenylenedimethanamine and 4,4′‐diaminodiphenylmethane were diazotized, and the obtained bis(diazonium) cations were coupled with 2,4‐dihydroxybenzaldehyde. The synthesized bis(diazo‐carbonyl) compounds, 5,5′‐((1,3‐phenylenebis(methylene))bis(diazene‐2,1‐diyl))bis(2,4‐dihydroxybenzaldehyde) (A1) and 5,5′‐((methylenebis(4,1‐phenylene))bis(diazene‐2,1‐diyl))bis(2,4‐dihydroxybenzaldehyde) (A2) were chemically supported on amino‐modified silica‐gel (as L1 and L2). Elemental analysis, liquid chromatography‐mass spectroscopy, liquid‐phase NMR (¹H and ¹³C) and solid‐phase NMR (CP‐MAS ²⁹Si and ¹³C), FT‐IR, TG/DTA, scanning electron microscopy and energy‐dispersive X‐ray spectroscopy techniques were used for characterizations of all the synthesized compounds. The syringe and batch techniques were applied for the solid‐phase extraction properties of Pb(II), Cu(II), Cd(II) and Cr(III) ions using an inductively coupled plasma‐atomic emission spectroscopy instrument. The recoveries of Pb(II), Cu(II), Cd(II) and Cr(III) ions have been achieved to 95–99% with the (RSDs) of ± 2–3% in optimum conditions.     

Synthesis,Characterization and Comparison of Properties of Novel Fluorinated Polyimides Derived from Bisphenol–A‐di(phthaleic anhydride)

Four new poly(etherimide)s have been synthesized by reaction with commercially available bisphenol‐A‐(diphthaleic anhydride) (BPADA) with four different kinds of diamines, namely 4,4′‐bis(p‐aminophenoxy‐3,3″‐trifluoromethyl) terphenyl,4,4′‐bis(3″‐trifluoromethyl‐p‐aminobiphenyl ether)biphenyl,2,6‐bis(3′‐trifluoromethyl‐p‐aminobiphenyl ether)pyridine, 2,5‐bis(3′‐trifluoromethyl‐p‐aminobiphenylether)thiopene. The poly(etherimide)s are named as 1a, 1b, 1c and 1d, respectively. The synthesized polyimides show good solubility in various organic solvents. The polyimide films had low water absorption of 0.19–0.30% and low dielectric constant of 2.79–3.1 at 1 MHz. These polyimides showed very high thermal stability with decomposition temperature (5% wt loss) up to 522°C in nitrogen. Transparent thin films of these polyimides exhibited tensile strength up to 97 MPa, a modulus of elasticity up to 1.56 GPa and elongation at break up to 20%.     

High‐Contrast Red–Green–Blue Tricolor Fluorescence Switching in Bicomponent Molecular Film

Highly efficient red–green–blue (RGB) tricolor luminescence switching was demonstrated in a bicomponent solid film consisting of (2Z,2′Z)‐2,2′‐(1,4‐phenylene)bis(3‐(4‐butoxyphenyl)acrylonitrile) (DBDCS) and (2Z,2′Z)‐3,3′‐(2,5‐bis(6‐(9H‐carbazol‐9‐yl)hexyloxy)‐1,4‐phenylene)bis(2‐(3,5‐bis(trifluoromethyl)phenyl)acrylonitrile) (m‐BHCDCS). Reversible RGB luminescence switching with a high ratiometric color contrast (λ_em=594, 527, 458 nm for red, green, and blue, respectively) was realized by different external stimuli such as heat, solvent vapor exposure, and mechanical force. It was shown that Förster resonance energy transfer in the bicomponent mixture could be efficiently switched on and off through supramolecular control.     

On the Reaction of Thiazole‐2,4‐diamines with Isothiocyanates – Preparation and Transformation of 2,4‐Diaminothiazole‐5‐carbothioamides

In the reaction of thiazole‐2,4‐diamines 8 with isothiocyanates 1 , 2,4‐diaminothiazole‐5‐carbothioamides 9, 10, 18 , and 19 as well as thiazolo[4,5‐d]pyrimidine‐7(6H)‐thiones 21 were formed. The carbothioamides 9, 10 , and 18 were transformed by reaction with different types of monofunctional and bifunctional electrophiles into hitherto unknown acceptor‐substituted 4,4′‐([2,5′‐bithiazole]‐2′,4′‐diyl)bis[morpholines] 24 and 29 , the 2′,4′‐bis(dialkylamino)[2,5′‐bithiazol]‐4‐(5H)‐ones 30 , and the 4‐substituted 2′,4′‐bis(dialkylamino)‐2,5′‐bithiazoles 31 . From 30 and 31 new 4‐mono‐ or 4,5‐disubstituted 2′,4′‐bis(dialkylamino)‐2,5′‐bithiazoles 34, 35, 38 , and 39 as well as 5‐substituted 2′,4′‐bis(dialkylamino)[2,5′‐bithiazol]‐4(5H)‐ones 33, 36 , and 37 were prepared.     

New blue electroluminescent n‐type polyfluorene copolymers with a 1,3,4‐oxadiazole unit in the main chain

Novel polyfluorene copolymers alternately having an 1,3,4‐oxadiazole unit in the main chain were prepared by both one‐step and two‐step methods for polyoxadiazole synthesis. They displayed highly efficient blue photoluminescence, the properties of which were affected by the extent of conjugation and the changes in the electron density by a side chain. An electrochemical analysis of the polymers using cyclic voltammetry suggested that they could be used as electron‐transport/hole‐blocking materials as well as blue emission materials for polymer light‐emitting diodes. A simple double‐layer device consisting of poly(N‐vinylcarbazole) as a hole‐transport layer and poly[(9,9′‐didodecylfluorene‐2,7‐diyl)‐alt‐((1,4‐bis(1,3,4‐oxadiazole)‐2,5‐di(2‐ethylhexyloxy)phenylene)‐5,5′‐diyl)] as an emission layer exhibited narrow blue electroluminescence with a maximum at 430 nm. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1058–1068, 2004     

Comparative study on polyimides from isomeric 3,3′‐, 3,4′‐, and 4,4′‐linked bis(thioether anhydride)s

Three isomeric bis(thioether anhydride) monomers, 4,4′‐bis(2,3‐dicarboxyphenylthio) diphenyl ketone dianhydride (3,3′‐PTPKDA), 4,4′‐bis(3,4‐dicarboxyphenylthio) diphenyl ketone dianhydride (4,4′‐PTPKDA), and 4‐(2,3‐dicarboxyphenylthio)‐4′‐(3,4‐dicarboxyphenylthio) diphenyl ketone dianhydride (3,4′‐PTPKDA), were prepared through multistep reactions. Their structures were determined via Fourier transform infrared, NMR, and elemental analysis. Three series of polyimides (PIs) were prepared from the obtained isomeric dianhydrides and aromatic diamines in N‐methyl‐2‐pyrrolidone (NMP) via the conventional two‐step method. The PIs showed excellent solubility in common organic solvents such as chloroform, N,N‐dimethylacetamide, and NMP. Their glass‐transition temperatures decreased according to the order of PIs on the basis of 3,3′‐PTPKDA, 3,4′‐PTPKDA, and 4,4′‐PTPKDA. The 5% weight loss temperatures (T_5%) of all PIs in nitrogen were observed at 504–519 °C. The rheological properties of isomeric PI resins based on 3,3′‐PTPKDA/4,4′‐oxydianiline/phthalic anhydride showed lower complex viscosity and better melt stability compared with the corresponding isomers from 4,4′‐ and 3,4′‐PTPKDA. In addition, the PI films based on three isomeric dianhydrides and 2,2′‐bis(trifluoromethyl)benzidine had a low moisture absorption of 0.27–0.35%. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Synthesis and properties of highly refractive polyimides derived from fluorene‐bridged sulfur‐containing dianhydrides and diamines

Highly refractive and transparent polyimides (PIs) based on fluorene‐bridged and sulfur‐containing monomers have been developed. An aromatic dianhydride, 4,4′‐[p‐thiobis(phenylenesulfanyl)]diphthalic anhydride (3SDEA), was polymerized with several fluorene‐containing diamines, including commercially available 9,9′‐bis(p‐aminophenyl)fluorene (APF), 9,9′‐bis[4‐(p‐aminophenoxy)phenyl]fluorene (OAPF), and newly synthesized 9,9′‐bis[4‐(p‐aminophenyl)sulfanylphenyl]fluorene (ASPF) to afford series A PIs. Meanwhile, series B PIs were obtained from a new dianhydride, 4,4′‐[(9H‐fluorene‐9‐ylidene)bis(p‐phenylsulfanyl)]diphthalic anhydride (FPSP) and two aromatic diamines, ASPF and 4,4′‐thiobis[(p‐phenylenesulfanyl)aniline] (3SDA) via a two‐step polycondensation procedure. The PIs exhibit good thermal stabilities, such as relatively high glass transition temperatures in the range of 220–270 °C and high initial thermal decomposition temperatures (T_10%) exceeding 490 °C. The 9,9′‐disubstituted fluorene moieties endow the PI films with good optical transparency. The optical transmittances of the PI films at 450 nm are all higher than 80% for the thickness of about 10 μm. Furthermore, the highly aromatic fluorene moiety and flexible thioether linkages in the molecular chains of the PIs provide them with high refractive indices of 1.6951–1.7258 and small birefringence of 0.0056–0.0070. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 1510–1520, 2008     

New Bis‐o‐Benzoquinoid Ligands with Ethylene Bridge and Their Metal Complexes

The treatment of di‐o‐quinone 4,4′‐(ethane‐1,2‐diyl)‐bis(3,6‐di‐tert‐butyl‐o‐benzoquinone) (Q–CH₂–CH₂–Q, 1 ) leads to its rearrangement to form di‐p‐quinomethide 4,4′‐(ethane‐1,2‐diylidene)bis(2‐hydroxy‐3,6‐di‐tert‐butyl‐cyclohexa‐2,5‐dienone) ( 2 ). The subsequent oxidation of 2 by an alkaline solution of K₃[Fe(CN)₆] yielded the new di‐o‐quinone 4,4′‐(ethene‐1,2‐diyl)bis(3,6‐di‐tert‐butyl‐o‐benzoquinone) (Q–CH=CH–Q, 3 ), which contains an ethylene bridge. The formation of mono‐ and poly‐reduced derivatives of 2 and 3 with potassium, thallium was studied by EPR technique. The dinuclear thallium derivative of 3 , Tl(SQ–CH=CH–SQ)Tl, was found to exist in the diamagnetic quinomethide form. The most stable derivatives of 2 and 3 are triphenyltin(IV) bis‐p‐quinomethide‐phenolate ( 4 ) and triphenylantimony(V) bis‐catecholate ( 5 ), which have been synthesized and isolated. The molecular structures of 2 , 3 , and 5 were characterized by single‐crystal X‐ray diffraction.     

Poly(arylene thioether) synthesis via nitro‐displacement reaction

High molecular weight poly(arylene thioether)s containing trifluoromethyl groups were prepared through the aromatic nucleophilic nitro‐displacement reaction of a dinitro monomer with aromatic dithiols. The high reactivity of the monomer, 4,4′‐dinitro‐3,3′‐bis(trifluoromethyl)biphenyl(1), activated by o‐trifluoromethyl groups and complete exclusion of oxygen was critical for the successful polymerization without any disulfide formation. The resulting trifluoromethylated poly(arylene thioether)s ( P1 and P2 ) were amorphous, dissolved in common organic solvents, and showed superior thermal properties compared to commercial poly(phenylene sulfide). © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2440–2447, 2006     

Synthesis and characterization of novel poly(amide‐imide)s containing 1,3‐diamino mesitylene moieties

A series of poly(amide‐imide)s were prepared using a new monomer, 1,3‐bis(trimellitimido)‐2,4,6‐trimethyl benzene (BTB), with four different diamines: 1,4‐phenylene diamine (PDA), 2,4‐diamino mesitylene (DAM), 2,2′‐dimethyl‐4,4′‐diamino biphenyl (DMDB), and 2,2′‐bis(trifluoromethyl)‐4,4′‐diamino biphenyl (TFDB). They were prepared by the condensation method in N‐methyl‐2‐pyrrolidinone (NMP) solvent using triphenyl phosphate and pyridine as condensing agents. The synthesized poly(amide‐imide)s were characterized by Fourier transform infrared and ¹H NMR techniques. Films were prepared and characterized using DSC, thermogravimetric analysis (TGA), a prism coupler, and a film dielectric property analyzer. DSC measurement showed that the glass‐transition temperatures of the polymers were in the range of 259–327 °C. TGA analysis showed 5% weight loss, in the range of 472–514 °C. The refractive index varied from 1.6004 to 1.6586 in the following increasing order: BTB‐TFBM < BTB‐DAM < BTB‐DMDB < BTB‐PDA. For the poly(amide‐imide) films, the birefringence varied in the range of 0.0319–0.0580, in the following increasing order: BTB‐DAM < BTB‐TFBM < BTB‐DMDB < BTB‐PDA. The capacitance method showed that the dielectric constant of poly(amide‐imide) varied with the diamine structure; no difference was found by the optical method. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 137–143, 2004     

Synthesis and comparison of the structure–property relationships of symmetric and asymmetric water‐soluble poly(p‐phenylene)s

Sodium salts of water‐soluble polymers poly{[2,5‐bis(3‐sulfonatopropoxy)‐1,4‐phenylene]‐alt‐[2,5‐bis(hexyloxy)‐1,4‐phenylene]} ( P1 ), poly{[2,5‐bis(3‐sulfonatopropoxy)‐1,4‐phenylene]‐alt‐[2,5‐bis(dodecyloxy)‐1,4‐phenylene]} ( P2 ), poly{[2,5‐bis(3‐sulfonatopropoxy)‐1,4‐phenylene]‐alt‐[2,5‐bis(dibenzyloxy)‐1,4‐phenylene]} ( P3 ), poly[2‐hexyloxy‐5‐(3‐sulfonatopropoxy)‐1,4‐phenylene] ( P4 ), and poly[2‐dodecyloxy‐5‐(3‐sulfonatopropoxy)‐1,4‐phenylene] ( P5 )] were synthesized with Suzuki coupling reactions and fully characterized. The first group of polymers ( P1 – P3 ) with symmetric structures gave lower absorption maxima [maximum absorption wavelength (λ_max) = 296–305 nm] and emission maxima [maximum emission wavelength (λ_em) = 361–398 nm] than asymmetric polymers P4 (λ_max = 329 nm, λ_em = 399 nm) and P5 (λ_max = 335 nm, λ_em = 401 nm). The aggregation properties of polymers P1 – P5 in different solvent mixtures were investigated, and their influence on the optical properties was examined in detail. Dynamic light scattering studies of the aggregation behavior of polymer P1 in solvents indicated the presence of aggregated species of various sizes ranging from 80 to 800 nm. The presence of alkoxy groups and 3‐sulfonatopropoxy groups on adjacent phenylene rings along the polymer backbone of the first set hindered the optimization of nonpolar interactions. The alkyl chain crystallization on one side of the polymer chain and the polar interactions on the other side allowed the polymers ( P4 and P5 ) to form a lamellar structure in the polymer lattice. Significant quenching of the polymer fluorescence upon the addition of positively charged viologen derivatives or cytochrome‐C was also observed. The quenching effect on the polymer fluorescence confirmed that the newly synthesized polymers could be used in the fabrication of biological and chemical sensors. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3763–3777, 2006     

PCPP derivatives containing carbazole pendant as hole transporting moiety for efficient blue electroluminescence

The syntheses and characterization of poly((2,6‐(4,4‐bis(4‐((2‐ethylhexyl)oxy)phenyl)‐4H‐cyclopenta[def]phenanthrene))‐co‐(2,6‐(4,4‐bis(4‐(((9‐carbazolyl)hexyl)oxy)phenyl))‐4H‐cyclopenta[def]phenanthrene)) (BCzPh‐PCPPs) and poly((2,6‐(4,4‐bis(4‐((2‐ethylhexyl)oxy)phenyl)‐4H‐cyclopenta[def]phenanthrene))‐co‐(2,6‐(4‐(4‐(((9‐carbazolyl)hexyl)oxy)phenyl)‐4‐(4‐((2‐ethylhexyl)oxy)phenyl)‐4H‐cyclopenta[def]phenanthrene))) (CzPh‐PCPPs), with carbazole unit as pendants, are presented. The carbazole moiety, which can improve the hole injection ability, was introduced as a pendant on the PCPP backbone. The devices of the polymers with the configurations of ITO/PEDOT:PSS/polymers/Ca/Al generate EL emission with maximum peaks at 400–450 nm, CIE coordinates of (x = 0.11–0.29, y = 0.11–0.33), low turn‐on voltages of 4–6 V, maximum brightness of 60–810 cd/m², and luminescence efficiencies of 0.04–0.22 cd/A. The PL spectra of CzPh‐PCPPs films did not show any peak at around 550 nm, which corresponds to keto defect or aggregate/excimer formation, even after annealing for 30 h at 150 °C in air. Out of the series, CzPh‐PCPP1 (PCPP derivative with 10% of carbazole moiety as pendant) shows blue emission with the maximum brightness of 810 cd/m² at 9 V, and the highest luminescence efficiency of 0.22 cd/A at 395 mA/cm². © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1327–1342, 2009     

Synthesis of new polyfluorene copolymers with a comonomer containing triphenylamine units and their applications in white‐light‐emitting diodes

Novel conjugated polyfluorene copolymers, poly[9,9‐dihexylfluorene‐2,7‐diyl‐co‐(2,5‐bis(4′‐diphenylaminostyryl)‐phenylene‐1,4‐diyl)]s (PGs), have been synthesized by nickel(0)‐mediated polymerization from 2,7‐dibromo‐9,9‐dihexylfluorene and 1,4′‐dibromo‐2,5‐bis(4‐diphenylaminostyryl)benzene with various molar ratios of the monomers. Because of the incorporation of triphenylamine (TPA) moieties, PGs exhibit much higher HOMO levels than the corresponding polyfluorene homopolymers and are able to facilitate hole injection into the polymer layer from the anode electrode in light‐emitting diodes. Conventional polymeric light‐emitting devices with the configuration ITO/PEDOT:PSS/polymer/Ca/Al have been fabricated. A light‐emitting device produced with one of the PG copolymers (PG10) as the emitting layer exhibited a voltage‐independent and stable bluish‐green emission with color coordinates of (0.22, 0.42) at 5 V. The maximum brightness and current efficiency of the PG10 device were 3370 cd/m² (at 9.6 V) and 0.6 cd/A, respectively. To realize a white polymeric light‐emitting diode, PG10 as the host material was blended with 1.0 wt % of a red‐light‐emitting polymer, poly[9,9‐dioctylfluorene‐2,7‐diyl‐alt‐2,5‐bis(2‐thienyl‐2‐cyanovinyl)‐1‐(2′‐ethylhexyloxy)‐4‐methoxybenzene‐5′,5′‐diyl] (PFR4‐S), and poly[2‐methoxy‐5‐(2′‐ethylhexyloxy)‐1,4‐phenylenevinylene] (MEH‐PPV). The device based on PG10:PFR4‐S showed an almost perfect pure white electroluminescence emission, with Commission Internationale de l'Eclairage (CIE) coordinates of (0.33, 0.36) at 8 V; for the PG10:MEH‐PPV device, the CIE coordinates at this voltage were (0.30, 0.40) with a maximum brightness of 1930 cd/m². Moreover, the white‐light emission from the PG10:PFR4‐S device was stable even at different driving voltages and had CIE coordinates of (0.34, 0.36) at 6 V and (0.31, 0.35) at 10 V. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1199–1209, 2007     

Synthesis and properties of fluorine‐containing polyethers with pendant hydroxyl groups by the polyaddition of bis(epoxide)s with diols

Fluorine‐containing polyethers with pendant hydroxyl groups were synthesized by the polyaddition of fluorine‐containing bis(epoxide)s with certain fluorine‐containing diols with quaternary onium salts as catalysts. When the polyaddition was performed with 2,2′,6,6′‐tetrafluoro‐4,4′‐biphenol diglycidiyl ether and 2,2′,6,6′‐tetrafluoro‐4,4′‐biphenol, the corresponding polyether with pendant hydroxyl groups was successfully obtained in good yield. The polyaddition of certain fluorine‐containing bis(epoxide)s with diols also proceeded in bulk to provide the corresponding fluorine‐containing polyethers with high molecular weights. These polyethers were highly transparent at 157 nm for 0.1 μm thickness, with their transmittance of 14–75% at 157 nm. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2543–2550, 2004