Journal of Polymer Research

, 26:30 | Cite as

Synthesis and properties of copolyarylenes containing indolo[3,2-b]carbazole moieties in the backbone

  • Oana Iuliana Negru
  • Mircea GrigorasEmail author


Three novel indolo[3,2-b]carbazole-based copolyarylenes were synthesized by Suzuki polycondensation of 6,12-di(4-bromophenyl)-5,11-dihydroindolo[3,2-b]carbazole with 2,5-thiophene diboronic acid, 2,5-bis(hexyloxy)phenyl-1,4-diboronic acid and 9,9-dihexylfluorene-2,7-diboronic acid bis(1,3-propanediol)ester. The molecular structure of the polymers was examined by FTIR, proton and carbon nuclear magnetic resonance spectroscopy methods. Their number average molecular weights range from 6300 to 8400 g·mol−1 and polydispersity indices are in the range 1.80–2.05. Thermal properties were studied by differential scanning calorimetry and thermogravimetric analysis. The photophysical and electrochemical properties were studied by UV-vis absorption spectroscopy, fluorescence spectroscopy and electrochemical methods. The results reveal that all polymers have high thermal stability with decomposition temperatures of 328 °C (P1), 350 °C (P2) and 378 °C (P3) and good electrochemical properties (high HOMO energy levels, air redox stability).

Graphical abstract

TGA curves of the polymers P1, P2 and P3.


Polyarylenes Indolo[3,2-b]carbazoles Optoelectronic properties Cyclic voltammetry 



  1. 1.
    Grazulevicius JP, Strohriegl P, Pielichowski J, Pielichowski K (2003) Carbazole-containig polymers: synthesis, properties and applications. Prog Polym Sci 28:1297–1353CrossRefGoogle Scholar
  2. 2.
    Bian L, Zhu E, Tang J, Tang W, Zhang F (2012) Recent progress in the design of narrow bandgap conjugated polymers for high-efficiency organic solar cells. Prog Polym Sci 37:1292–1331CrossRefGoogle Scholar
  3. 3.
    Bouldreault PLT, Beaupré S, Leclerc M (2010) Polycarbazoles for plastic electronics. Polym Chem 1:127–136CrossRefGoogle Scholar
  4. 4.
    Morin JF, Leclerc M, Adès D, Siove A (2005) Polycarbazoles: 25 years of progress. Macromol Rapid Commun 26:761–778CrossRefGoogle Scholar
  5. 5.
    Karon K, Lapkowski M (2015) Carbazole electrochemistry: a short review. J Solid State Electrochem 19:2601–2611CrossRefGoogle Scholar
  6. 6.
    Guo X, Baumgarten M, Müllen K (2013) Designing π-conjugated polymers for organic electronics. Prog Polym Sci 38:1832–1908CrossRefGoogle Scholar
  7. 7.
    Gendron D, Leclerc M (2011) New conjugated polymers for plastic solar cells. Energy Environ Sci 4:1225–1237CrossRefGoogle Scholar
  8. 8.
    Grigalevicius S (2006) 3,6(2,7),9-substituted carbazoles as electroactive amorphous materials for optoelectronics. Synth Met 156:1–12CrossRefGoogle Scholar
  9. 9.
    Blouin N, Leclerc M (2008) Poly(2,7-carbazole)s: structure-property relationships. Acc Chem Res 41:1110–1119PubMedCrossRefGoogle Scholar
  10. 10.
    Wakin S, Aϊch BR, Tao Y, Leclerc M (2008) Charge transport, photovoltaic, and thermoelectric properties of poly(2,7-carbazole) and poly(indolo[3,2-b]carbazole) derivatives. Polym Rev 48:432–462CrossRefGoogle Scholar
  11. 11.
    Hu NX, Xie S, Popovic ZD, Ong B, Hor AM (2000) Novel high T g hole-transport molecules based on indolo[3,2-b]carbazoles for organic light-emitting devices. Synth Met 111–112:421–424Google Scholar
  12. 12.
    Shi H, Yang J, Dong X, Fang L, Dong C, Choi MMF (2013) A novel asymmetric indolo[3,2-b]carbazole derivative containing benzothiazole and dimesitylboron units: synthesis, photophysical and sensing properties. Synth Met 179:42–48CrossRefGoogle Scholar
  13. 13.
    Shi H, Yuan J, Wu X, Dong X, Fang L, Miao Y, Wang H, Cheng F (2014) Two novel indolo[3,2-b]carbazole derivatives containing dimesitylboron moieties: synthesis, photoluminescent and electroluminescent properties. New J Chem 38:2368–2378CrossRefGoogle Scholar
  14. 14.
    Lengvinaite S, Grazulevicius JV, Grigalevicius S, Gu R, Dehaen W, Jankauskas V, Zhang B, Xie Z (2010) Indolo[3,2-b]carbazole-based functional derivatives as materials for light emitting diodes. Dyes Pigments 85:183–188CrossRefGoogle Scholar
  15. 15.
    Kirkus M, Grazulevicius JV, Grigalevicius S, Gu R, Dehaen W, Jankauskas V (2009) Hole-transporting glass-forming indolo[3,2-b]carbazole-based diepoxy monomer and polymers. Eur Polym J 45:410–417CrossRefGoogle Scholar
  16. 16.
    Simokaitiene J, Stanislovaityte E, Grazulevicius JV, Jankauskas V, Gu R, Dehaen W, Hung YC, Hsu CP (2012) Synthesis and properties of methoxyphenyl-substituted derivatives of Indolo[3,2-b]carbazole. J Org Chem 77:4924–4931PubMedCrossRefGoogle Scholar
  17. 17.
    Wakim S, Bouchard J, Simard M, Drolet N, Tao Y, Leclerc M (2004) Organic microelectronics: design, synthesis, and characterization of 6,12-dimethylindolo[3,2-b]carbazoles. Chem Mater 16:4386–4388CrossRefGoogle Scholar
  18. 18.
    Li Y, Wu Y, Ong BS (2006) Polyindolo[3,2-b]carbazoles: a new class of p-channel semiconductor polymers for organic thin-film transistors. Macromolecules 39:6521–6527CrossRefGoogle Scholar
  19. 19.
    Lee WY, Chen CW, Chueh CC, Yang CC, Chen WC (2008) Synthesis of new fluorine-indolocarbazole alternating copolymers for light-emitting diodes and field effect transistors. Polym J 40:249–255CrossRefGoogle Scholar
  20. 20.
    Tsai JH, Chueh CC, Lai MH, Wang CF, Chen WC, Ko BT, Ting C (2009) Synthesis of new indolocarbazole-acceptor alternating conjugated copolymers and their applications to thin film transistors and photovoltaic cells. Macromolecules 42:1897–1905CrossRefGoogle Scholar
  21. 21.
    Li Y, Wu Y, Gardner S, Ong BS (2005) Novel peripherally substituted indolo[3,2-b]carbazoles for high-mobility organic thin-film transistors. Adv Mater 17:849–853CrossRefGoogle Scholar
  22. 22.
    Boudreault PLT, Wakim S, Blouin N, Simard M, Tessier C, Tao Y, Leclerc M (2007) Synthesis, characterization, and application of indolo[3,2-b]carbazole semiconductors. J Am Chem Soc 129:9125–9136PubMedCrossRefGoogle Scholar
  23. 23.
    Boudreanu PLT, Wakim S, Tang ML, Tao Y, Bao Z, Leclerc M (2009) New indolo[3,2-b]carbazole derivatives for field-effect transistor applications. J Mater Chem 19:2921–2928CrossRefGoogle Scholar
  24. 24.
    Bintinger J, Yang S, Fruhmann P, Holzer B, Stöger B, Svirkova A, Marchetti-Deschmann M, Horkel E, Hametner C, Fröhlich J, Kymissis I, Mikula H (2017) Synthesis, characterization and printing application of alkylated indolo[3,2-b]carbazoles. Synth Met 228:9–17CrossRefGoogle Scholar
  25. 25.
    Zhong W, Xu J, Sun S, Liang J, Zhang B, He R, Lan L, Huang F, Ying L, Yang W, Peng J, Cao Y (2015) Effects of bride units on the propertirs of indolo[3,2-b]carbazole-co-difluorobenzo[d][1,2,3]triazole based π-conjugated copolymers. Org Electron 23:17–27CrossRefGoogle Scholar
  26. 26.
    Xiao Z, Di Y, Tan Z, Cheng X, Chen B, Feng J (2016) Efficient organic dyes based on perpendicular 6,12-diphenyl substituted indolo[3,2-b]carbazole donor. Photochem Photobiol Sci 15:1514–1523PubMedCrossRefGoogle Scholar
  27. 27.
    Su JY, Lo CY, Tsai CH, Chen CH, Chou SH, Liu SH, Chou PT, Wong KT (2014) Indolo[2,3-b]carbazole synthesized from a double-intramolecular Buchwald-Hartwig reaction: its application for a dianchor DSSC organic dye. Org Lett 16:3176–3179PubMedCrossRefGoogle Scholar
  28. 28.
    Cai S, Tian G, Li X, Su J, Tian H (2013) Efficient and stable DSSC sensitizers based on substituted dihydroindolo[2,3-b]carbazole donor with high molar extinction coefficients. J Mater Chem A 1:11295–11305CrossRefGoogle Scholar
  29. 29.
    Zhang XH, Wang ZS, Cui Y, Koumura N, Furube A, Hara K (2009) Organic sensitizers based on hexylthiophene-functionalized indolo[3,2-b]carbazole for efficient dye-sensitized solar cells. J Phys Chem C 113:13409–13415CrossRefGoogle Scholar
  30. 30.
    Peng Q, Liu X, Qiu Y, Xu J, Li M, Dai L (2011) Pyrazino[2,3-g]quinoxaline-based conjugated copolymers with indolocarbazole coplanar moieties designed for efficient photovoltaic applications. J Mater Chem 21:7714–7722CrossRefGoogle Scholar
  31. 31.
    Zhou E, Yamakawa S, Zhang Y, Tajima K, Yang C, Hashimoto K (2009) Indolo[3,2-b]carbazole-based alternating donor-acceptor copolymers: synthesis, properties and photovoltaic application. J Mater Chem 19:7730–7737CrossRefGoogle Scholar
  32. 32.
    Lu J, Liang F, Drolet N, Ding J, Tao Y, Movileanu R (2008) Crystalline low band-gap alternating indolocarbazole and benzothiadiazole-cored oligothiophene copolymer for organic solar cell applications. Chem Commun 42:5315–5317CrossRefGoogle Scholar
  33. 33.
    Sharma B, Sarothia Y, Singh R, Kan Z, Keivanidis PE, Jacob J (2016) Synthesis and characterization of light-absorbing cyclopentadithiophene-based donor-acceptor copolymers. Polym Int 65:57–65CrossRefGoogle Scholar
  34. 34.
    Chan LH, Lin LC, Yao CH, Liu YR, Jiang ZJ, Cho TY (2013) Synthesis of indolo[3,2-b]carbazole-based random copolymers for polymer solar cell applications. Thin Solid Films 544:386–391CrossRefGoogle Scholar
  35. 35.
    Chen S, Yu H, Zhao C, Hu R, Zhu J, Li L (2017) Indolo[3,2-b]carbazole derivative as a fluorescent probe for fluoride ion and carbon dioxide detections. Sensors Actuators B Chem 250:591–600CrossRefGoogle Scholar
  36. 36.
    Zhang J, Chen Z, Wang XY, Guo SZ, Dong YB, Yu GA, Yin J, Liu SH (2017) Redox-modulated near-infrared electrochromism, electroluminochromism, and aggregation-induced fluorescence change in an indolo[3,2-b]carbazole-bridged diamine system. Sensors Actuators B Chem 246:570–577CrossRefGoogle Scholar
  37. 37.
    Gokce G, Ozkut MI (2018) An indolocarbazole based yellow-to-cyan soluble electrochromic polymer. Org Electron 52:317–322CrossRefGoogle Scholar
  38. 38.
    Gu R, Snick SV, Robeyns K, Meervelt LV, Dehaen W (2009) A facile and general method for the synthesis of 6,12-diaryl-5,11-dihydroindolo[3,2-b]carbazoles. Org Biomol Chem 7:380–385PubMedCrossRefGoogle Scholar
  39. 39.
    Van Snick S, Dehaen W (2012) Synthesis of novel 2,8-disubstituted indolo[3,2-b]carbazoles. Org Biomol Chem 10:79–82PubMedCrossRefGoogle Scholar
  40. 40.
    Blouin N, Michaud A, Wakim S, Boudreault PLT, Leclerc M, Vercelli B, Zecchin S, Zotti G (2006) Optical, electrochemical, magnetic, and conductive properties of new polyindolocarbazoles and polydiindolocarbazoles. Macromol Chem Phys 207:166–174CrossRefGoogle Scholar
  41. 41.
    Levesque I, Bertrand PO, Blouin N, Leclerc M, Zecchin S, Zotti G, Ratcliffe CI, Klug DD, Gao X, Gao F, Tse JS (2007) Synthesis and thermoelectric properties of polycarbazole, polyindolocarbazole, and polydiindolocarbazole derivatives. Chem Mater 19:2128–2138CrossRefGoogle Scholar
  42. 42.
    Blouin N, Leclerc M, Vercelli B, Zecchin S, Zotti G (2006) Optical, electrochemical, magnetic, and conductive properties of new poly(indolocarbazole-alt-bithiophene)s. Macromol Chem Phys 207:175–182CrossRefGoogle Scholar
  43. 43.
    Grigoras M, Negru OI, Solonaru AM (2015) Indolo[3,2-b]carbazole-based poly(arylene ethynylene)s: modulation of their optoelectronic properties by changing the position of substituents. High Perform Polym 27:571–582CrossRefGoogle Scholar
  44. 44.
    Negru OI, Solonaru AM, Grigoras M (2016) Indolo[3,2-b]carbazole-based poly(arylene vinylene)s. the influence of substitution position on spectroscopic and electrochemical properties. Polym Int 65:1449–1457CrossRefGoogle Scholar
  45. 45.
    Miyaura N, Suzuki A (1995) Palladium-catalyzed cross-coupling reactions of organoboron compounds. Chem Rev 95:2457–2483CrossRefGoogle Scholar
  46. 46.
    Gronowitz S, Hörnfeldt AB (1991) Thiophene and its derivatives – Part Four- Chapter: Physical properties of thiophene derivatives. This is a part of the forty fourth volume in the series: The Chemistry Of Heterocyclic Compunds, E. C. Taylor, A. Weissberger Editors. John Wiley & Sons. Inc.Google Scholar
  47. 47.
    Shi H, Shi L, Dai J, Xu L, Wang M, Wu X, Fang L, Dong C, Choi MMF (2012) Synthesis, photophysical and electrochemical properties and theoretical studies on three novel indolo[3,2-b]carbazole derivatives containing benzothiazole units. Tetrahedron 68:9788–9794CrossRefGoogle Scholar
  48. 48.
    Chen S, Wei J, Wang K, Wang C, Chen D, Liu Y, Wang Y (2013) Constructing high-performance blue, yellow and red electroluminescent devices based on a class of multifunctional organic materials. J Mater Chem C 1:6594–6602CrossRefGoogle Scholar
  49. 49.
    Taniguchi M, Lindsey JS (2018) Database of absorption and fluorescence spectra of >300 common compounds for use in PhotochemCAD. Photochem Photobiol 94:290–327PubMedCrossRefGoogle Scholar
  50. 50.
    Garmshausen Y, Schwarz J, Hildebrandt J, Kobin B, Pätzel M, Hecht S (2014) Making nonsymmetrical bricks: synthesis of insoluble dipolar sexiphenyls. Org Lett 16:2838–2841PubMedCrossRefGoogle Scholar
  51. 51.
    van Hutten PF, Brouwer HJ, Krasnikov VV, Ouali L, Stalmach U, Hadziioannou G (1999) Effect of solid-state structure on optical properties of conjugated organic materials. Synth Met 102:1443–1446CrossRefGoogle Scholar
  52. 52.
    Shi H, Dai J, Wu X, Shi L, Yuan J, Fang L, Miao Y, Du X, Wang H, Dong C (2013) A novel dimesitylboron-substituted indolo[3,2-b]carbazole derivative: synthesis, electrochemical, photoluminescent and electroluminescent properties. Org Electron 14:868–874CrossRefGoogle Scholar
  53. 53.
    Brédas JL, Silbey R, Boudreaux DS, Chance RR (1983) Chain-length dependence of electronic and electrochemical properties of conjugated systems: polyacetylene, polyphenylene, polythiophene, and polypyrrole. J Am Chem Soc 105:6555–6559CrossRefGoogle Scholar

Copyright information

© The Polymer Society, Taipei 2019

Authors and Affiliations

  1. 1.Electroactive Polymers Department“P. Poni” Institute of Macromolecular ChemistryIasiRomania

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