Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 51 Issue 20

October 2013

Volume 51, Issue 20

Pages i–iv, 4241–4488

  1. Cover Image

    1. Top of page
    2. Cover Image
    3. Highlights
    4. Rapid Communications
    5. Articles
    1. You have free access to this content
      Cover Image, Volume 51, Issue 20 (pages i–ii)

      Article first published online: 13 SEP 2013 | DOI: 10.1002/pola.26911

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      Organic π-conjugated polymers such as poly(3-alkylthiophene)s are widely investigated for their interesting chemical and electrical properties. The electron transport characteristics of these materials are strongly dependent on their regioregularity. In that respect, a new synthetic approach is developed by Laura Ricciotti et al. on page 4351 to make regioregular poly[3-(4-alkoxyphenyl)thiophene]s by following an innovative, easy, and cost-effective synthetic route. Four copper(II) complexes are synthesized and used as catalysts to obtain polymers with very high regioregular head-tail insertion, comparable to that obtained by oxidative coupling methodologies reported in the literature. These polymers show reasonably good hole mobility in bottom contact field-effect transistors, up to 4 × 10−4 cm2 volt−1sec−1.

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      Cover Image, Volume 51, Issue 20 (pages iii–iv)

      Article first published online: 13 SEP 2013 | DOI: 10.1002/pola.26912

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      PolyHIPEs are polymers with highly interconnected porous structures synthesized within high internal phase emulsion (HIPE) templates. This image represents work by Michael S. Silverstein et al. on page 4369 on a polystyrene-based polyHIPE synthesized within a water-in-oil HIPE that contains an aqueous carbon nanotube (CNT) dispersion in its internal phase. The CNTs migrate into the oil phase during polymerization and are found within the polymer walls. Emulsion polymerization takes place within the micelles formed by the dispersion's water-soluble surfactant, producing polymer nanoparticles (PNPs) that deposit on the polyHIPE walls during drying. In this composition, the CNTs within the polymer walls (transmission electron micrograph) are seen through the holes in the PNP-covered polymer walls (scanning electron micrograph).

  2. Highlights

    1. Top of page
    2. Cover Image
    3. Highlights
    4. Rapid Communications
    5. Articles
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      Diketopyrrolopyrrole-based conjugated polymers and small molecules for organic ambipolar transistors and solar cells (pages 4241–4260)

      Mallari A. Naik and Satish Patil

      Article first published online: 10 JUL 2013 | DOI: 10.1002/pola.26843

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      The present work discusses the development and use of diketopyrrolopyrrole (DPP)-based conjugated polymers in organic electronic research. The figure gives glimpses of some important DPP based polymeric systems. The device architecture in the bottom left corner shows that DPP polymers are used as donor and fullerene based materials as acceptor. The energy level diagram located in the center shows how the split in band gap takes place upon absorbing sunlight. All these major observations and achievements made from the use of DPP by various research groups are summarized in the highlight.

  3. Rapid Communications

    1. Top of page
    2. Cover Image
    3. Highlights
    4. Rapid Communications
    5. Articles
    1. Efficient stabilization of thiol-ene formulations in radical photopolymerization (pages 4261–4266)

      Paricher Esfandiari, Samuel Clark Ligon, Jean Jacques Lagref, Richard Frantz, Zoubair Cherkaoui and Robert Liska

      Article first published online: 7 AUG 2013 | DOI: 10.1002/pola.26848

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      Various phenolic radical inhibitors were tested to improve storage stability of thiol-ene formulations. After determining the optimal inhibitor, a synergetic effect was discovered when it was used in combination with acidic buffer, thus preventing premature dark gelation while maintaining desired photoreactivity.

  4. Articles

    1. Top of page
    2. Cover Image
    3. Highlights
    4. Rapid Communications
    5. Articles
    1. Novel regular polyimide-graft-(polymethacrylic acid) brushes: Synthesis and possible applications as nanocontainers of cyanoporphyrazine agents for photodynamic therapy (pages 4267–4281)

      Alexander V. Yakimansky, Tamara K. Meleshko, Dmitrii M. Ilgach, Maria A. Bauman, Tatiana D. Anan'eva, Larisa G. Klapshina, Svetlana A. Lermontova, Irina V. Balalaeva and William E. Douglas

      Article first published online: 19 JUL 2013 | DOI: 10.1002/pola.26846

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      Novel regular polyimide brushes with poly(t-butyl-methacrylate) and poly(methacrylic acid) side chains were synthesized, using ATRP from polyimide multicenter initiators. It is shown that polyimide-graft-poly(methacrylic acid) copolymers are efficient nanocontainers for cyanoporphirazines, which may be used as photodynamic therapy agents

    2. Engineering of new crosslinked near-infrared fluorescent polyethylene glycol bisphosphonate nanoparticles for bone targeting (pages 4282–4291)

      Eran Gluz, Igor Grinberg, Enav Corem-Salkmon, Dana Mizrahi and Shlomo Margel

      Article first published online: 22 JUL 2013 | DOI: 10.1002/pola.26858

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      New functional near-IR fluorescent crosslinked poly(PEG–Bisphosphonates) nanoparticles were prepared. The size of these nanoparticles was controlled by changing various polymerization parameters. A chicken embryo model was used for an in vivo biodistribution study of the NIR fluorescent poly(PEG–BP) nanoparticles. Results indicated that the fluorescence intensity of all organs (e.g., blood, spleen, liver, kidney, and heart) except the bones decreased significantly within 48 h while that of the bones hardly changed over that time.

    3. Aminimides derived from p-substituted benzoylformic acid ester as thermal/photolatent bases and photoradical initiators (pages 4292–4300)

      Manabu Kirino and Ikuyoshi Tomita

      Article first published online: 6 JUL 2013 | DOI: 10.1002/pola.26838

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      Aminimides, 1,1-dimethyl-1-(2-hydroxypropyl)amine benzoylformimide derivatives possessing substituents at the p-position, were synthesized as thermal/photolatent bases and photoradical initiators, and their activity was evaluated in the polymerizations of the epoxide/thiol system and the vinyl monomer. The thermal base activity was found to increase by the electron-donating substituents on the benzene ring. The photobase/photoradical activity was also found to be affected by the substituents, where the p-methoxy substituent facilitated both the base and the radical initiating ability.

    4. Heterogeneous polycondensation for composition control of poly(p-mercaptobenzoyl-co-p-benzamide) by shearing (pages 4301–4308)

      Toshimitsu Ichimori, Shinichi Yamazaki and Kunio Kimura

      Article first published online: 6 JUL 2013 | DOI: 10.1002/pola.26839

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      Composition control of aromatic poly(thioester–amide) was examined by reaction–induced phase separation during polymerization. Poly(thioester–amide)s were obtained as precipitates and the content of amide moiety in them became lower than that in the feed by shearing owing to the shearing effect on reaction rate and solubility of oligomers.

    5. Synthesis of photocleavable poly(methyl methacrylate-block-d-lactide) via atom-transfer radical polymerization and ring-opening polymerization (pages 4309–4316)

      Hong Li, Sahas Rathi, Elizabeth S. Sterner, Hui Zhao, Shaw Ling Hsu, Patrick Theato, Yongming Zhang and E. Bryan Coughlin

      Article first published online: 10 JUL 2013 | DOI: 10.1002/pola.26840

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      A well-defined photocleavable block copolymer containing an ortho-nitrobenzyl (ONB) linker between poly(methyl methacrylate) (PMMA) and poly(d-lactide) (PDLA) blocks is synthesized and characterized. The photocleavage of the copolymers occurs under mild conditions by simple irradiation with 302 nm wavelength UV light for several hours.

    6. Synthesis and characterization of azo–bisbenzylidene-based polymers for second order nonlinear optics (pages 4317–4324)

      Balakrishna Kolli, Someshwarnath Pandey, Sarada P. Mishra, Tapan Kanai, Mukesh P. Joshi, Raj S. Mohan, Tham Singh Dhami, Lalit Mohan Kukreja and Asit Baran Samui

      Article first published online: 10 JUL 2013 | DOI: 10.1002/pola.26842

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      Main chain polymers containing dual nonlinear optics active moieties azo and bisbenzylidene were synthesized by polycondensation method. In addition, bisbenzylidene has the ability to crosslink the polymer chains under irradiation to enhance the stability after poling. The second-harmonic generation intensity was found to remain stable up to about 90 °C. The cross–linking behavior was also studied by irradiating with UV light.

    7. Relevance of linked dye-coinitiator in visible three-component photoinitiating systems: Application to red light photopolymerization (pages 4325–4330)

      Koichi Kawamura, Christian Ley, Julien Schmitt, Maxime Barnet and Xavier Allonas

      Article first published online: 17 JUL 2013 | DOI: 10.1002/pola.26844

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      An original red light photoinitiating system (PIS) for free radical polymerization containing a dye–acceptor coinitiator dyad (S–TA) and a nondissociative electron donor (Fc) was evaluated. An increased rate of free radical polymerization of acrylates in film was observed, due to faster intramolecular electron transfer in dyads. Competitive two step oxidative (red)/reductive (blue) paths electron transfer processes enhance the efficiency of free radical generation leading to higher photopolymerization rates.

    8. Hyperbranched polyphosphoesters with reactive end groups synthesized via acyclic diene metathesis polymerization and their transformation to crosslinked nanoparticles (pages 4331–4340)

      Liang Ding, Jun Qiu, Rong Lu, Xueqin Zheng and Jing An

      Article first published online: 29 JUL 2013 | DOI: 10.1002/pola.26845

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      Novel hyperbranched polyphosphoesters (HBPPEs) with a variety of peripheral acrylate groups were synthesized via acyclic diene metathesis polymerization based on a newly phosphate–containing AB2 monomer. The limiting oxygen index values up to 26.9 were obtained for HBPPEs, showing an increase in the flame–retardant properties of HBPPEs. These reactive HBPPEs were then converted into a new type of permanent nanoparticle with comparatively uniform size by means of an intramolecular crosslinking reaction.

    9. Mesogen-controlled ion channel of star-shaped hard–soft block copolymers for solid-state lithium-ion battery (pages 4341–4350)

      Yongfen Tong, Lie Chen, Xiaohui He and Yiwang Chen

      Article first published online: 17 JUL 2013 | DOI: 10.1002/pola.26847

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      Novel star-shaped triblock liquid crystalline copolymers are prepared by atom-transfer radical polymerization. Nanoscale phase separation morphologies are achieved by cooperative assembly of the hard polystyrene inner sphere, the polyethyleneoxide middle sphere, and mesogen-containing end chains. Uniform self-assembly morphologies are improved by thermal annealing from the liquid crystalline states. The mesogen-controlled ion channel has been achieved and the ionic conductivities are greatly increased owing to the orderly continuous channel. The lithium-ion battery shows better lithium ion transference number and electrochemical stability.

    10. Synthesis of highly regioregular poly[3-(4-alkoxyphenyl)-thiophene]s by oxidative catalysis using copper complexes (pages 4351–4360)

      Laura Ricciotti, Fabio Borbone, Antonio Carella, Roberto Centore, Antonio Roviello, Mario Barra, Giuseppina Roviello, Claudio Ferone, Carla Minarini and Pasquale Morvillo

      Article first published online: 19 JUL 2013 | DOI: 10.1002/pola.26849

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      A novel, easy, and cost-effective synthesis is reported for the production of very highly regioregular poly[3-(4-alkoxyphenyl)thiophene]s by means of oxidative coupling. Four copper complexes were synthesized and used as catalysts to obtain polymers with regioregularity much higher than that obtained by previous oxidative coupling methodologies reported in the literature. Their regioregularity was investigated by UV–Visible characterization on polymer thin films and 1H-NMR analysis. The polymers show reasonably high mobility up to 4 × 10−4 cm2 V−1 s−1.

    11. Reversible addition–fragmentation chain-transfer polymerization of vinyl monomers with N,N-dimethyldiselenocarbamates (pages 4361–4368)

      Dimitri Matioszek, Oleksii Brusylovets, D. James Wilson, Stéphane Mazières and Mathias Destarac

      Article first published online: 17 JUL 2013 | DOI: 10.1002/pola.26850

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      N,N–dimethyldiselenocarbamates are successfully used as reversible addition–fragmentation chain–transfer agents to mediate the polymerization of acrylate, vinyl ester, and N–vinylcaprolactam monomers. The transfer activity of these derivatives is close to that of sulfur–based dithiocarbamate counterparts. Complementary analytical techniques, including 2D 77Se/1H NMR, bring evidence of the controlled character of vinyl acetate polymerization. This process allows the preparation of poly(acrylate)–poly(vinyl acetate) diblock copolymers.

    12. Carbon nanotubes in emulsion-templated porous polymers: Polymer nanoparticles, sulfonation, and conductivity (pages 4369–4377)

      Noa Cohen, Dikla Cohen Samoocha, Dganit David and Michael S. Silverstein

      Article first published online: 27 JUL 2013 | DOI: 10.1002/pola.26851

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      Porous polystyrene-based polyHIPEs were synthesized within a water-in-oil high internal phase emulsion (HIPE) containing an aqueous carbon nanotube (CNT) dispersion. The polymer nanoparticle–covered polyHIPE structure reflects two simultaneous polymerizations, within the external phase and within monomer-swollen water-soluble surfactant micelles. The CNTs migrated from the internal phase and formed interconnected bundles within the polyHIPE walls. The conductivity of the hygroscopic sulfonated polyHIPE was significantly enhanced by the formation of CNT “bridges” between the existing conductive pathways.

    13. Cu(0)/2,6-bis(imino)pyridines catalyzed single-electron transfer-living radical polymerization of methyl methacrylate initiated with poly(vinylidene fluoride-co-chlorotrifluoroethylene) (pages 4378–4388)

      Xin Hu, Junjie Li, Huayi Li and Zhicheng Zhang

      Article first published online: 19 JUL 2013 | DOI: 10.1002/pola.26853

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      A series of 2,6-bis(imino)pyridines, as common ligands for late transition metal catalyst in ethylene coordination polymerization, were successfully employed in SET-LRP of MMA by using P(VDF-co-CTFE) as macroinitiator with low concentration of copper catalyst under relatively mild reaction conditions. The relationship between the catalytic activity and chemical structure of 2,6-bis(imino)pyridine ligands was investigated by comparing both the electrochemical properties of Cu(II)/2,6-bis(imino)pyridine and the kinetics results of SET-LRP of MMA catalyzed with different ligands.

    14. Synthesis of anionic amphiphilic diblock copolymers of poly(styrene) and poly(acrylic acid) by reverse iodine transfer polymerization (RITP) in solution and emulsion (pages 4389–4398)

      David Rayeroux, Braja N. Patra and Patrick Lacroix-Desmazes

      Article first published online: 19 JUL 2013 | DOI: 10.1002/pola.26852

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      Reverse iodine transfer polymerization (RITP) presents numerous benefits as compared to other common CRP techniques as far as the synthesis of amphiphilic block copolymers is concerned. Taking advantage of its simplicity which stems from the in situ generation of transfer agents, RITP was applied in solution and emulsion to the synthesis of anionic amphiphilic diblock copolymers of poly(styrene) and poly(acrylic acid) from the easy cleavable tert-butyl acrylate precursor.

    15. A new thermo-responsive block copolymer with tunable upper critical solution temperature and lower critical solution temperature in the alcohol/water mixture (pages 4399–4412)

      Yang Su, Meihan Dan, Xin Xiao, Xiaohui Wang and Wangqing Zhang

      Article first published online: 19 JUL 2013 | DOI: 10.1002/pola.26854

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      The multi–thermo–responsive block copolymer of poly[2–(2–methoxyethoxy)ethyl methacrylate]–b–poly[N–(4–vinylbenzyl)–N,N–diethylamine] (PMEO2MA–b–PVEA) undergoes phase transition at LCST or UCST in the alcohol/water mixture, and various block copolymer morphologies including inverted micelles, core–corona micelles, and corona–collapsed micelles are prepared by adjusting the water content in the solvent.

    16. Soluble and transparent polyimides from unsymmetrical diamine containing two trifluoromethyl groups (pages 4413–4422)

      Sun Dal Kim, Sang Youl Kim and Im Sik Chung

      Article first published online: 15 JUL 2013 | DOI: 10.1002/pola.26855

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      A new unsymmetrical diamine monomer containing two trifluoromethyl (CF3) groups is prepared and polymerized with typical dianhydrides to produce the corresponding polyimides (PIs). The PIs show excellent solubility and good optical transparency together with high Tg values, high thermal stability, and low refractive indexes due to the unsymmetrical presence of two CF3 groups in rigid PIs.

    17. Synthesis and properties of cationic ionomers from poly(ester-urethane)s based on polylactide (pages 4423–4428)

      Yuushou Nakayama, Takamichi Inaba, Yosuke Toda, Ryo Tanaka, Zhengguo Cai, Takeshi Shiono, Hiroyuki Shirahama and Chikara Tsutsumi

      Article first published online: 26 JUL 2013 | DOI: 10.1002/pola.26857

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      Poly(l-lactide)-based poly(ester-urethane)s (PEU) with equally spaced tertiary amine groups were prepared by l-lactide polymerization initiated with N-methyldiethanolamine followed by chain-extension with hexamethylene diisocyanate. Treatment of the PEUs with iodomethane afforded cationic ionomers (PEU-MeI) with quaternary ammonium groups. Their thermal, mechanical, hydrophilic, and biodegradation properties were investigated.

    18. Thermosensitive t-PLA-b-PNIPAAm tri-armed star block copolymer nanoscale micelles for camptothecin drug release (pages 4429–4439)

      Feng Xu, Shu-Zhen Zheng and Yan-Ling Luo

      Article first published online: 22 JUL 2013 | DOI: 10.1002/pola.26859

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      A thermosensitive tri-armed star-shaped block copolymer has been synthesized by the ring-opening polymerization of d,l-lactide, followed by ATRP of NIPAAm. The copolymers can self-assemble into nanoscale micelles in aqueous solution, and their physicochemical properties depend on the copolymer compositions, micelle concentrations, and media. The copolymer micelles are low cytotoxicity and safe, and exhibit a thermo-triggered CPT drug targeting release behavior, and thus have potential application values in drug controlled delivery.

    19. pH-responsive polymer core–shell nanospheres for drug delivery (pages 4440–4450)

      Hui Wang and Garry L. Rempel

      Article first published online: 19 JUL 2013 | DOI: 10.1002/pola.26860

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      Schematic diagram illustrating the synthesis (Stage 1), surfactant removal (Stage 2), and pyrene release (Stage 3) of pyrene-loaded poly(DEAEMA)–poly(PEGMA) core–shell nanospheres. The release of pyrene from the core–shell polymer matrix can be triggered by a change in the environmental pH. In particular the pyrene-loaded nanospheres are capable of responding to a narrow window of pH change from pH = 5, 6, to 7 and can achieve a significant pyrene release of above 80% within 90 h.

    20. Synthesis of amphiphilic block copolymer by metal-free ring-opening oligomerization of glycidyl phenyl ether initiated with tetra-n-butylammonium fluoride in the presence of poly(ethylene glycol) monomethyl ether (pages 4451–4458)

      Hisatoyo Morinaga, Yusuke Ujihara and Takeshi Endo

      Article first published online: 22 JUL 2013 | DOI: 10.1002/pola.26861

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      Metal-free amphiphilic block copolymer was successfully obtained by the ring-opening oligomerization of glycidyl phenyl ether (GPE) initiated with tetra-n-butylammonium fluoride (n-Bu4NF) in the presence of poly(ethylene glycol) monomethyl ether as a chain transfer agent. The resulting amphiphilic block copolymers isolated by filtration of the aqueous polymer solution could undergo self-association in aqueous media to form micelles.

    21. Fluorescence emission of amphiphilic copolymers bearing benzimidazole groups: Stimuli-responsive behaviors in aqueous solution (pages 4459–4466)

      Bing Han, Nianchen Zhou, Wei Zhang, Zhenping Cheng, Jian Zhu and Xiulin Zhu

      Article first published online: 22 JUL 2013 | DOI: 10.1002/pola.26864

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      A stimuli-responsive fluorescent copolymer poly(NIPAMm-b-VBNBIn) was designed and synthesized by reversible addition–fragmentation chain transfer polymerization. The aqueous solutions of the copolymers exhibited reversible fluorescence responses to pH and temperature.

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      Branched polyphosphazenes with controlled dimensions (pages 4467–4473)

      Helena Henke, Sandra Wilfert, Aitziber Iturmendi, Oliver Brüggemann and Ian Teasdale

      Article first published online: 29 JUL 2013 | DOI: 10.1002/pola.26865

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      Highly branched polyphosphazenes are prepared with controlled chains lengths, branch lengths, and number of branches. The polymers are water soluble and biodegradable, making them good candidates for biomedical applications.

    23. Fast-activated anionic polymerization of ε-caprolactam in the bulk under quasi-adiabatic conditions: Comparison of different kinetic models (pages 4474–4480)

      Saverio Russo, Sabrina Maniscalco, Paolo Moretti and Laura Ricco

      Article first published online: 23 JUL 2013 | DOI: 10.1002/pola.26866

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      The synthesis of polyamide 6 from ε-caprolactam by the activated anionic route is generating relevant interest in innovative applications. Therefore, it is necessary to have available a reliable model for the kinetic description of polymerization. The present study not only explores how experimental conditions can be used for discrimination among various kinetic models, but also supports some very recent findings on the applicability of the Kamal–Sourour model to the activated anionic polymerization of ε-caprolactam.

    24. Synthesis and characterization of copolymers based on cyclopenta[c]thiophene and bithiazole and their transistor properties (pages 4481–4488)

      Anjan Bedi, Satyaprasad P. Senanayak, K. S. Narayan and Sanjio S. Zade

      Article first published online: 31 JUL 2013 | DOI: 10.1002/pola.26867

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      Two new polymers comprising cyclopenta[c]thiophene (CPT) and bithiazole (BTz) are synthesized and fully characterized. P2, composed of thiophene spaced CPT and BTz units possesses lower band gap and higher hole mobility (µh) of 0.052 cm2 V−1 s−1 with current on/off ratio (Ion/Ioff) in the order of 103. The insertion of two additional thiophene rings improves the morphology, µh, and extent of self-aggregation in the solid state.

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