Skip to main content
SpringerLink
Log in

Synthesis of hyperbranched conjugated polymers based on 3-hexylthiophene, triphenylamine and benzo [c] [1,2,5] thiadiazole moieties: convenient synthesis through suzuki polymerization and impact of structures on optical properties

  • Original Paper
  • Published:
Journal of Polymer Research Aims and scope Submit manuscript

Abstract

Novel 3-hexylthiophene-based hyperbranched conjugated polymers containing triphenylamine and benzo [c] [1, 2, 5] thiadiazole moieties were synthesized by Suzuki coupling polymerization of tris (4-bromophenyl) amine, 2,2′-(3-hexylthiophene-2,5-diyl) bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane) and 4,7-dibromobenzo [c] [1, 2, 5] thiadiazole. Organic solvent-soluble polymers with number-average molecular weights of 24,000 and 42,000 g/mol were obtained in 54–57 % yields. Their structures, molecular weights and thermal properties were characterized via proton nuclear magnetic resonance (1H NMR) and Fourier transform infrared (FT-IR) spectroscopies, gel permeation chromatography (GPC), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and wide-angle powder X-ray diffraction (XRD) measurements. Optical investigation by UV–vis and fluorescence spectroscopies revealed that the incorporation of the benzo [c] [1, 2, 5] thiadiazole moiety in the hyperbranched polymer structure resulted in a red-shift of the maximum absorption wavelength and an increase in the solution-photoluminescence quantum yield, indicating an extension of the conjugation length. The UV–vis, DSC and XRD results demonstrated that the aggregation of conjugated polymer chains could effectively be reduced by the hyperbranched structures and that conjugation length extension via the introduction of benzo [c] [1, 2, 5] thiadiazole units led to the coexistence of both crystalline and amorphous phases in the solid state and in solution upon addition of a non-solvent.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Scheme. 1
Scheme. 2
Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7

Similar content being viewed by others

References

  1. McCullough RD, Tristram-Nagle S, Williams SP, Lowe RD, Jayaraman M (1993) Self-orienting head-to-tail poly (3-alkylthiophenes): new insights on structure–property relationships in conducting polymers. J Am Chem Soc 115:4910–4911

    Article  CAS  Google Scholar 

  2. Chen T-A, Wu X, Rieke RD (1995) Regiocontrolled synthesis of poly (3-alkylthiophenes) mediated by Rieke Zinc: their characterization and solid-state properties. J Am Chem Soc 117:233–244

    Article  CAS  Google Scholar 

  3. Bao Z, Dodabalapur A, Lovinger AJ (1996) Soluble and processable regioregular poly (3-hexylthiophene) for thin film field-effect transistor applications with high mobility. Appl Phys Lett 69:4108–4110

    Article  CAS  Google Scholar 

  4. Sirringhaus H, Tessler N, Friend RH (1998) Integrated optoelectronic devices based on conjugated polymers. Science 280:1741–1744

    Article  CAS  Google Scholar 

  5. Agrawal AK, Jenekhe SA (1993) Synthesis and processing of heterocyclic polymers as electronic, optoelectronic, and nonlinear optical materials. 2. New series of conjugated rigid-rod polyquinolines and polyanthrazolines. Macromolecules 26:895–905

    Article  CAS  Google Scholar 

  6. Hancock JM, Gifford AP, Champion RD, Jenekhe SA (2008) Block Co-oligomers for Organic Electronics and Optoelectronics: Synthesis, Photophysics, Electroluminescence, and Field-Effect Charge Transport of Oligothiophene-b-oligoquinoline-b-oligothiophene Triblock Co-oligomers. Macromolecules 41:3588–3597

    Article  CAS  Google Scholar 

  7. Arias AC, MacKenzie JD, McCulloch I, Rivnay J, Salleo A (2010) Materials and applications for large area electronics: solution-based approaches. Chem Rev 110:3–24

    Article  CAS  Google Scholar 

  8. Pron A, Gawrys P, Zagorska M, Djurado D, Demadrille R (2010) Electroactive materials for organic electronics: preparation strategies, structural aspects and characterization techniques. Chem Soc Rev 39:2577–2632

    Article  CAS  Google Scholar 

  9. Pan H, Wu Y, Li Y, Liu P, Ong BS, Zhu S, Xu G (2007) Benzodithiophene copolymer—A low-temperature, solution-processed high-performance semiconductor for thin-film transistors. Adv Funct Mater 17:3574–3579

    Article  CAS  Google Scholar 

  10. Li Y, Wu Y, Liu P, Birau M, Pan H, Ong BS (2006) Poly (2,5-bis (2-thienyl) -3,6-dialkylthieno [3,2-b] thiophene)s—High-mobility semiconductors for thin-film transistors. Adv Mater 18:3029–3032

    Article  CAS  Google Scholar 

  11. Chen L, Li X, Ying W, Zhang X, Guo F, Li J, Hua J (2013) 5,6-Bis (octyloxy) benzo [c] [1,2,5] thiadiazole-bridged dyes for dye-sensitized solar cells with high open-circuit voltage performance. Eur J Org Chem 2013:1770–1780

    Article  CAS  Google Scholar 

  12. Ma F, Shi W, Mi H, Luo J, Lei Y, Tian Y (2013) Triphenylamine-based conjugated polymer/I − complex as turn-on optical probe for mercury (II) ion. Sensors Actuators B Chem 182:782–788

    Article  CAS  Google Scholar 

  13. Lim ZB, Xue B, Bomma S, Li H, Sun S, Lam YM, Belcher WJ, Dastoor PC, Grimsdale AC (2011) New moderate bandgap polymers containing alkoxysubstituted-benzo [c] [1,2,5] thiadiazole and thiophene-based units. J Polym Sci A Polym Chem 49:4387–4397

    Article  CAS  Google Scholar 

  14. Reisch A, Komber H, Voit B (2007) Kinetic Analysis of Two Hyperbranched A2 + B3 Polycondensation Reactions by NMR Spectroscopy. Macromolecules 40:6846–6858

    Article  CAS  Google Scholar 

  15. Krämer M, Kopaczynska M, Krause S, Haag R (2007) Dendritic polyamine architectures with lipophilic shells as nanocompartments for polar guest molecules: A comparative study of their transport behavior. J Polym Sci A Polym Chem 45:2287–2303

    Article  Google Scholar 

  16. Paul GK, Mwaura J, Argun AA, Taranekar P, Reynolds JR (2006) Cross-linked hyperbranched arylamine polymers as hole-transporting materials for polymer LEDs. Macromolecules 39:7789–7792

    Article  CAS  Google Scholar 

  17. Dong H, Zheng R, Lam JWY, Häussler M, Qin A, Tang BZ (2005) A new route to hyperbranched macromolecules: syntheses of photosensitive poly (aroylarylene)s via 1,3,5-regioselective polycyclotrimerization of bis (aroylacetylene)s. Macromolecules 38:6382–6391

    Article  CAS  Google Scholar 

  18. Sun M, Li J, Li B, Fu Y, Bo Z (2005) Toward high molecular weight triphenylamine-based hyperbranched polymers. Macromolecules 38:2651–2658

    Article  CAS  Google Scholar 

  19. Sunder A, Mülhaupt R, Haag R, Frey H (2000) Hyperbranched polyether polyols: a modular approach to complex polymer architectures. Adv Mater 12:235–239

    Article  CAS  Google Scholar 

  20. Liou G-S, Lin H-Y, Yen H-J (2009) Synthesis and characterization of electroactive hyperbranched aromatic polyamides based on A2B-type triphenylamine moieties. J Mater Chem 19:7666–7673

    Article  CAS  Google Scholar 

  21. Bo Z, Schluter AD (2003) “AB2 + AC2” approach to hyperbranched polymers with a high degree of branching. Chemical Communications 2354–2355

  22. J.H obson L, M. Kenwright A (1997) A simple ‘one pot’ route to the hyperbranched analogues of Tomalia's poly (amidoamine) dendrimers. Chemical Communications 1877–1879

  23. Smet M, Schacht E, Dehaen W (2002) Synthesis, characterization, and modification of hyperbranched poly (arylene oxindoles) with a degree of branching of 100 %. Angew Chem Int Ed 41:4547–4550

    Article  CAS  Google Scholar 

  24. Bharathi P, Moore JS (2000) controlled synthesis of hyperbranched polymers by slow monomer addition to a core. Macromolecules 33:3212–3218

    Article  CAS  Google Scholar 

  25. Ishida Y, Sun ACF, Jikei M, M-a K (2000) Synthesis of hyperbranched aromatic polyamides starting from dendrons as ABx monomers: effect of monomer multiplicity on the degree of branching. Macromolecules 33:2832–2838

    Article  CAS  Google Scholar 

  26. Li B, Li J, Fu Y, Bo Z (2004) Porphyrins with four monodisperse oligofluorene arms as efficient red light-emitting materials. J Am Chem Soc 126:3430–3431

    Article  CAS  Google Scholar 

  27. Kanibolotsky AL, Berridge R, Skabara PJ, Perepichka IF, Bradley DDC, Koeberg M (2004) Synthesis and properties of monodisperse oligofluorene-functionalized truxenes: highly fluorescent star-shaped architectures. J Am Chem Soc 126:13695–13702

    Article  CAS  Google Scholar 

  28. Tour JM (1996) Conjugated macromolecules of precise length and constitution organic synthesis for the construction of nanoarchitectures. Chem Rev 96:537–554

    Article  CAS  Google Scholar 

  29. Belletête M, Bouchard J, Leclerc M, Durocher G (2005) Photophysics and solvent-induced aggregation of 2,7-carbazole-based conjugated polymers. Macromolecules 38:880–887

    Article  Google Scholar 

  30. Li K, Wang Q (2004) Synthesis and solution aggregation of polystyrene − oligo (p-phenyleneethynylene) − polystyrene triblock copolymer. Macromolecules 37:1172–1174

    Article  CAS  Google Scholar 

  31. Bouchard J, Belletête M, Durocher G, Leclerc M (2003) Solvatochromic properties of 2,7-carbazole-based conjugated polymers. Macromolecules 36:4624–4630

    Article  CAS  Google Scholar 

  32. Ma H, Liu S, Luo J, Suresh S, Liu L, Kang SH, Haller M, Sassa T, Dalton LR, Jen AKY (2002) Highly efficient and thermally stable electro-optical dendrimers for photonics. Adv Funct Mater 12:565–574

    Article  CAS  Google Scholar 

  33. Qu J, Shiotsuki M, Kobayashi N, Sanda F, Masuda T (2007) Synthesis and properties of carbazole-based hyperbranched conjugated polymers. Polymer 48:6481–6490

    Article  CAS  Google Scholar 

  34. Li J, Sun M, Bo Z (2007) Synthesis of hyperbranched polymers with precise conjugation length. J Polym Sci A Polym Chem 45:1084–1092

    Article  CAS  Google Scholar 

  35. Okamoto K, Housekeeper JB, Michael FE, Luscombe CK (2013) Thiophene based hyperbranched polymers with tunable branching using direct arylation methods. Polym Chem 4:3499–3506

    Article  CAS  Google Scholar 

  36. He Q, Huang H, Yang J, Lin H, Bai F (2003) Synthesis and spectroscopic properties of a series of hyperbranched conjugated molecules with 1,3,5-triphenylbenzene as cores. J Mater Chem 13:1085–1089

    Article  CAS  Google Scholar 

  37. Hollamby MJ, Nakanishi T (2013) The power of branched chains: optimising functional molecular materials. J Mater Chem C 1:6178–6183

    Article  CAS  Google Scholar 

  38. Wang H-S, Su M-S, Wei K-H (2010) Synthesis and characterization of donor–acceptor poly (3-hexylthiophene) copolymers presenting 1,3,4-oxadiazole units and their application to photovoltaic cells. J Polym Sci A Polym Chem 48:3331–3339

    Article  CAS  Google Scholar 

  39. Zen A, Saphiannikova M, Neher D, Grenzer J, Grigorian S, Pietsch U, Asawapirom U, Janietz S, Scherf U, Lieberwirth I, Wegner G (2006) Effect of molecular weight on the structure and crystallinity of poly (3-hexylthiophene). Macromolecules 39:2162–2171

    Article  CAS  Google Scholar 

  40. Kim J (2002) Assemblies of conjugated polymers Intermolecular and intramolecular effects on the photophysical properties of conjugated polymers. Pure Appl Chem 74:2031–2044

    Article  CAS  Google Scholar 

  41. Sonar P, Singh SP, Sudhakar S, Dodabalapur A, Sellinger A (2008) High-mobility organic thin film transistors based on benzothiadiazole-sandwiched dihexylquaterthiophenes. Chem Mater 20:3184–3190

    Article  CAS  Google Scholar 

  42. Sonar P, Singh SP, Leclere P, Surin M, Lazzaroni R, Lin TT, Dodabalapur A, Sellinger A (2009) Synthesis, characterization and comparative study of thiophene-benzothiadiazole based donor-acceptor-donor (D-A-D) materials. J Mater Chem 19:3228–3237

    Article  CAS  Google Scholar 

  43. Verploegen E, Miller CE, Schmidt K, Bao Z, Toney MF (2012) Manipulating the morphology of P3HT–PCBM bulk heterojunction blends with solvent vapor annealing. Chem Mater 24:3923–3931

    Article  CAS  Google Scholar 

  44. Zha D, Chen L, Wu F, Wang H, Chen Y (2013) Donor–acceptor-integrated conjugated polymers based on carbazole [3,4-c:5,6-c] bis [1,2,5] thiadiazole with tight π–π stacking for photovoltaics. J Polym Sci, Part A: Polym Chem 51:565–574

    Article  CAS  Google Scholar 

  45. Bredas JL, Heeger AJ (1990) Theoretical investigation of gas-phase torsion potentials along conjugated polymer backbones: polyacetylene, polydiacetylene, and polythiophene. Macromolecules 23:1150–1156

    Article  CAS  Google Scholar 

  46. Gettinger CL, Heeger AJ (1994) The effect of intrinsic rigidity on the optical properties of PPV derivatives. Mol Cryst Liq Cyst 256:507–512

    Article  CAS  Google Scholar 

  47. DiCésare N, Belletête M, Leclerc M, Durocher G (1999) Intermolecular Interactions in Conjugated Oligothiophenes. 2. Quantum Chemical Calculations Performed on Crystalline Structures of Terthiophene and Substituted Terthiophenes. J Phys Chem A 103:803–811

    Article  Google Scholar 

  48. Ruini A, Caldas MJ, Bussi G, Molinari E (2002) Solid state effects on exciton states and optical properties of PPV. Phys Rev Lett 88:206403

    Article  Google Scholar 

  49. Ferretti A, Ruini A, Molinari E, Caldas MJ (2003) Electronic properties of polymer crystals: the effect of interchain interactions. Phys Rev Lett 90:086401

    Article  Google Scholar 

Download references

Acknowledgments

This research was fully supported by Vietnam National Foundation for Science and Technology Development (NAFOSTED) under grant number “104.02-2013.18”.

Author information

Authors and Affiliations

  1. Faculty of Materials Technology, Ho Chi Minh City University of Technology, Vietnam National University, 268 Ly Thuong Kiet, District 10, Ho Chi Minh City, Vietnam

    Ha Tran Nguyen, Le-Thu T. Nguyen, Trung Thanh Nguyen, Anh Tuan Luu & Thang Van Le

Authors
  1. Ha Tran Nguyen
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Le-Thu T. Nguyen
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Trung Thanh Nguyen
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Anh Tuan Luu
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Thang Van Le
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Ha Tran Nguyen.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Nguyen, H.T., Nguyen, LT.T., Nguyen, T.T. et al. Synthesis of hyperbranched conjugated polymers based on 3-hexylthiophene, triphenylamine and benzo [c] [1,2,5] thiadiazole moieties: convenient synthesis through suzuki polymerization and impact of structures on optical properties. J Polym Res 21, 552 (2014). https://doi.org/10.1007/s10965-014-0552-y

Download citation

  • Received:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1007/s10965-014-0552-y

Keywords

Search

Navigation