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Synthesis and morphological characterization of a new conjugated polymer based on benzobisoxazole and thiophene systems

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Abstract

In the present work, the synthesis, electropolymerization and polymer characterization of 2,6-di(4-butylphenyl)-4,8-dithiophenylbenzobisoxazole are reported. The synthesis involves several steps from 1,4-benzoquinone to form 2,5-diamine-3,6-dibromohydroquinone, which is condensed with 4-butylbenzoyl chloride and later with thiophen-2-ylmagnesium bromide through Kumada coupling reactions. This monomer is polymerized by potentiodynamic cyclic voltammetry. The voltammograms show a dependency on the range of applied potential, and three different processes of thermodynamically reversible oxidation and reduction occur on a platinum surface. Theoretical calculations are used to characterize these redox processes. The distribution of the frontier orbital density for the monomer and trimer forms show the participation of the thiophene ring in the polymerization processes and partial oxidation of the benzoxazole fragment. The characterization of the polymeric deposit was carried out by scanning electron microscopy and Raman spectroscopy. A dependence of both the morphology and vibrational state of the polymer on the potential range applied exists. This is attributed to the different conformations and dihedral angles of the macromolecule. Finally, the optical properties of the material indicate the existence of intramolecular charge transfer through the system’s thiophene and benzobisoxazole (donor and acceptor).

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References

  1. Hains AW, Liang Z, Woodhouse MA, Gregg BA (2010) Molecular semiconductors in organic photovoltaic cells. Chem Rev 110:6689–6735

    Article  CAS  Google Scholar 

  2. Cheng YJ, Yang SH, Hsu CS (2009) Synthesis of conjugated polymers for organic solar cell applications. Chem Rev 109:5868–5923

    Article  CAS  Google Scholar 

  3. Bujak P, Kulszewicz-Bajer I, Zagorska M, Maurel V, Wielgus I, Pron A (2013) Polymers for electronics and spintronics. Chem Soc Rev 42:8895–8999

    Article  CAS  Google Scholar 

  4. Carbasa B, Odabasb S, Türksoy F, Tanyelic C (2016) Synthesis of a new electrochromic polymer based on tetraphenylethylene core tetrakis carbazole complex and its electrochromic device application. Electrochim Acta 103:72–79

    Article  Google Scholar 

  5. Carbas B, Asil D, Friend R, Önal A (2014) A new blue light emitting and electrochromic polyfluorene derivative for display applications. Org Electron 15:500–508

    Article  CAS  Google Scholar 

  6. Chu TY, Lu JP, Beaupre S, Zhang YG, Pouliot JR, Wakim S, Zhou J, Leclerc M, Li Z, Ding J, Tao Y (2011) Bulk heterojunction solar cells using thieno[3,4-c]pyrrole-4,6-dione and dithieno[3,2-b:20,30-d]silole copolymer with a power conversion efficiency of 7.3%. J Am Chem Soc 133:4250–4253

    Article  CAS  Google Scholar 

  7. Li YF, Zou YP (2008) Conjugated polymer photovoltaic materials with broad absorption band and high charge carrier mobility. Adv Mater 20:2952–2958

    Article  CAS  Google Scholar 

  8. Roncali J, Thobie-Gautier C (1994) An efficient strategy towards small bandgap polymers: the rigidification of the π-conjugated system. Adv Mater 6:846–848

    Article  CAS  Google Scholar 

  9. Pei Q, Zuccarello G, Ahlskog M, Inganas O (1994) Electrochromic and highly stable poly(3,4-ethylenedioxythiophene) switches between opaque blue-black and transparent sky blue. Polymer 35:1347–1351

    Article  CAS  Google Scholar 

  10. McCulloch I, Ashraf RS, Biniek L, Bronstein H, Combe C, Donaghey JE, James DI, Nielsen CB, Schroeder BC, Zhang W (2012) Design of semiconducting indacenodithiophene polymers for high performance transistors and solar cells. Acc Chem Res 45:714–722

    Article  CAS  Google Scholar 

  11. Zhou H, Liu LYS, You W (2010) A tale of current and voltage: interplay of band gap and energy levels of conjugated polymers in bulk heterojunction solar cells. Macromolecules 43:10390–10396

    Article  CAS  Google Scholar 

  12. Chen HY, Hou J, Hayden AE, Yang H, Houk KN, Yang Y (2010) Silicon atom substitution enhances interchain packing in a thiophene-based polymer system. Adv Mater 22:371–375

    Article  CAS  Google Scholar 

  13. Carbas B, Kivrak A, Teke E, Zora M, Önal A (2014) Electrochemical polymerization of a new low-voltage oxidized thienylenepyrrole derivative and its electrochromic device application. J Electroanal Chem 729:15–20

    Article  CAS  Google Scholar 

  14. Skoteheim TA, Elsenbaumer RL, Reynolds JR (1998) Handbook of conducting polymers, chapter 4, 2nd edn. Marcel Dekker, New York, pp 531–588

    Google Scholar 

  15. Smith MK, Singh V, Kalaitzidou K, Cola BA (2016) High thermal and electrical conductivity of template fabricated P3HT/MWCNT composite nanofibers. ACS Appl Mater Interfaces 8:14788–114794

    Article  CAS  Google Scholar 

  16. Wolfe JF, Arnold FE (1981) Rigid-rod polymer. 1. synthesis and thermal properties of para-aromatic polymers with 2,6-benzobisoxazole units in the main chain. Macromolecules 14:909–915

    Article  CAS  Google Scholar 

  17. Wolfe JF, Loo BH, Arnold FE (1981) Rigid-rod polymers. 2. synthesis and thermal properties of para-aromatic polymers with 2,6-benzobisthiazole units in the main chain. Macromolecules 14:915–920

    Article  CAS  Google Scholar 

  18. So YH, Martin SJ, Bell B, Pfeiffer CD, Van Effen RM, Romain BL, Lefkowitz SM (2003) Importance of π-stacking in photoreactivity of aryl benzobisoxazole and aryl benzobisthiazole compounds. Macromolecules 36:4699–4708

    Article  CAS  Google Scholar 

  19. Wolfe F (1988) Encyclopedia of polymer science and engineering, vol 11. Wiley, New York, p 601

    Google Scholar 

  20. Osaheni JA, Jenekhe SA (1994) Efficient blue luminescence of a conjugated polymer exciplex. Macromolecules 27:739–742

    Article  CAS  Google Scholar 

  21. Wang S, Chen Y, Zhuang Q, Li X, Wu P, Han Z (2006) Competition between host aggregates and isolated guest chromophores in trapping excitons in polybenzazole copolymers and blends. Macromol Chem Phys 207:2336–2342

    Article  CAS  Google Scholar 

  22. Wu CC, Tsay PY, Cheng HY, Bai SJ (2004) Polarized luminescence and absorption of highly oriented, fully conjugated, heterocyclic aromatic rigid-rod polymer poly-p-phenylenebenzobisoxazole. J Appl Phys 95:417–423

    Article  CAS  Google Scholar 

  23. Jenekhe SA, Osaheni JA, Meth JS, Vanherzeele H (1992) Nonlinear optical properties of poly(p-phenylenebenzobisoxazole). Chem Mater 4:683

    Article  CAS  Google Scholar 

  24. Reinhardt BA, Unroe MR, Evers RC (1991) Third-order optical nonlinearities of model compounds containing benzobisthiazole, benzobisoxazole, and benzbisimidazole units. Chem Mater 3:864–871

    Article  CAS  Google Scholar 

  25. Intemann JJ, Hellerich ES, Tlach BC, Ewan MD, Barnes CA, Bhuwalka A, Cai M, Shinar J, Shinar R, Jeffries-EL M (2012) Altering the conjugation pathway for improved performance of benzobisoxazole-based polymer guest emitters in polymer light-emitting diodes. Macromolecules 45:6888–6897

    Article  CAS  Google Scholar 

  26. Saeed AEM, Omer MA (2009) Synthesis of some 2,5-diamino-3,6-dibromo -1,4-benzoquinones. Afr J Pure Appl Chem 12:275–280

    Google Scholar 

  27. Hegedus LS, Odle RR, Winton PM, Weider PR (1982) Synthesis of 2,5-disubstituted 3,6-diamino-1,4-benzoquinones. J Org Chem 47:2607–2613

    Article  Google Scholar 

  28. Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Scalmani G, Barone V, Mennucci B, Petersson GA, Nakatsuji H, Caricato M, Li X, Hratchian HP, Izmaylov AF, Bloino J, Zheng G, Sonnenberg JL, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Vreven T, Montgomery JAJ, Peralta JE, Ogliaro F, Bearpark M, Heyd JJ, Brothers E, Kudin KN, Staroverov VN, Kobayashi R, Normand J, Raghavachari K, Rendell A, Burant JC, Iyengar SS, Tomasi J, Cossi M,. Rega N, Millam JM, Klene M, Knox JE, Cross JB, Bakken V, Adamo C, Jaramillo J, Gomperts R, Stratmann RE, Yazyev O, Austin AJ, Cammi R, Pomelli C, Ochterski JW, Martin RL, Morokuma K, Zakrzewski VG, Voth GA, Salvador P, Dannenberg JJ, Dapprich S, Daniels AD, Farkas Ö, Foresman JB, Ortiz JV, Cioslowski J, Fox DJ (2010) Gaussian 09, Revision A.1

  29. Skotheim TA, Reynolds JR (eds) (2007) Handbook of conducting polymers, chapter 2, vol 1, 3rd edn. CRC Press, Boca Raton, p 9-1

    Google Scholar 

  30. Inzelt G (2008) Conducting polymers a new era in electrochemistry, chapter 2, 2nd edn. Springer, Heidelberg, pp 480–530

    Google Scholar 

  31. Chen X, Inganäs O (1996) Three-step redox in polythiophenes: evidence from electrochemistry at an ultramicroelectrode. J Phys Chem 100:15202–15206

    Article  CAS  Google Scholar 

  32. Heinze J, Frontana-Uribe BA, Ludwigs S (2010) Electrochemistry of conducting polymers—persistent models and new concepts. Chem Rev 110:4724–4771

    Article  CAS  Google Scholar 

  33. Kurowska A, Kostyuchenko AS, Zassowski P, Skorka L, Yurpalov VL, Fisyuk AS, Pron A, Domagala W (2014) Symmetrically disubstituted bithiophene derivatives of 1, 3, 4-oxadiazole, 1,3,4-thiadiazole, and 1,2,4-triazole—spectroscopic, electrochemical, and spectroelectrochemical properties. J Phys Chem C 118:25176–25189

    Article  CAS  Google Scholar 

  34. Bazzaoui EA, Marsault JP, Aeiyach S, Lacaze PC (1994) Resonance Raman study of polythiophene films in the doped and undoped states. Relations between spectral data and physicochemical properties. Synth Met 66:217–224

    Article  CAS  Google Scholar 

  35. Baibarac M, Baltog I, Smaranda I, Scocioreanu M, Mevellec JY, Lefrant S (2014) Abnormal anti-Stokes Raman scattering and surface-enhanced infrared absorption spectroscopy studies of carbon nanotubes electrochemically functionalized with poly(2,2′-bithiophene-co-pyrene). Appl Surf Sci 309:11–21

    Article  CAS  Google Scholar 

  36. Kang H, Zhao B, Cao Z, Zhong J, Li H, Pei Y, Shen P, Tan S (2013) Synthesis and photovoltaic properties of conjugated copolymers with benzo[1,2-b:4,5-b′]dithiophene and thiadiazolo[3,4-c]pyridine moieties. Eur Polym J 49:2738–2747

    Article  CAS  Google Scholar 

  37. Jin JK, Choi JK, Kim BJ, Kang HB, Yoon SC, You H, Jung HT (2011) Synthesis and photovoltaic performance of low-band gap polymers on the basis of 9,9-dialkyl-3,6-dialkyloxysilafluorene. Macromolecules 44:502–511

    Article  CAS  Google Scholar 

  38. Gadisa A, Mammo W, Andersson LM, Admassie S, Zhang F, Andersson MR, Inganas O (2007) A new donor–acceptor–donor polyfluorene copolymer with balanced electron and hole mobility. Adv Funct Mater 17:3836–3842

    Article  CAS  Google Scholar 

  39. Jespersen KG, Beenken WJD, Zaushitsyn Y, Yartsev A, Andersson M, Pullerits T, Sundstrom V (2004) The electronic states of polyfluorene copolymers with alternating donor–acceptor units. J Chem Phys 121:12613–12617

    Article  CAS  Google Scholar 

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Acknowledgements

The authors acknowledge financial support from Pontificia Universidad Católica de Valparaíso, DII Grant No. 039.340/2016 and are also grateful to CONICYT-FONDEQUIP program NMR 300, Grant No. EQM 130154, and FONDECYT Grant No. 1140810, ECOS-CONICYT Grant No. C14E05 and CONICYT—Beca Doctorado Nacional No. 21140238.

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  1. Instituto de Química, Facultad de Ciencias, Pontificia Universidad Católica de Valparaíso, Av. Brasil 2950, Valparaíso, Chile

    Juan Carlos Ahumada, Patricio Leyton, Juliet Andrea Aristizabal & Juan Pablo Soto

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  1. Juan Carlos Ahumada
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Correspondence to Juan Pablo Soto.

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Ahumada, J.C., Leyton, P., Aristizabal, J.A. et al. Synthesis and morphological characterization of a new conjugated polymer based on benzobisoxazole and thiophene systems. Polym. Bull. 75, 597–610 (2018). https://doi.org/10.1007/s00289-017-2057-4

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