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Triphenylamine based redox-active, fluorescent polyamides: synthesis and photophysics


An electroactive series of polyamides was synthesized from 4,4′-diamino-4′′-phenoxy triphenylamine (1), 4,4′-diamino-4′′-benzyloxy triphenylamine (2) and terephthaloyl or isophthaloyl chloride. The FTIR (Fourier Transform Infrared) spectral characterization and solubility test of the subsequent polyamides (PA I-IV), UV-vis, photoluminescence spectral analysis (PL) and cyclic voltammetry were utilized to assess photophysical and electrochemical properties of the materials. The oxidative-thermal stability of the polyamides as judged by thermogravimetric analysis was found to be in the range 438-532 °C with the char yield more than 53% at 800 °C. Introduction of aryloxy triphenylamine units along with polymer backbone flexibility improved the organosolubility of the synthesized polyamides (PA I-IV). The appreciable organosolubility of the (PA I-IV) is enough to be used in coating applications such as inkjet printing. Bluish green light emission from our synthesized materials upon excitation at 375 nm is credited to the triphenylamine linked amide-based polymer chain. Both pendent phenoxy and benzyloxy groups at para position in (PA I-IV) have also elevated the HOMO energy levels and hence lowered the onset oxidation potential. Additionally, the computational analysis was also conducted to get optimized ground-state geometry by DFT method (B3LYP) with 6-31G basis set. The 3-dimensional distributions of both HOMO (Highest Occupied Molecular Orbital) and LUMO (Lowest Unoccupied Molecular Orbital) of the polymers were obtained. The computational data of the polymers also augmented the experimental data suggesting their future use as redox-active materials.

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  1. 1.

    Iwan A, Sek D (2011) Polymers with triphenylamine units: photonic and electroactive materials. Prog Polym Sci 36:1277–1325.

  2. 2.

    Lin HY, Liou GS, Lee WY, Chen WC (2007) Poly (triarylamine): its synthesis, properties, and blend with polyfluorene for white-light electroluminescence. J Polym Sci A Polym Chem 45:1727–1736.

  3. 3.

    Chiu KY, Su TX, Li JH, Lin TH, Liou GS, Cheng SH (2005) Novel trends of electrochemical oxidation of amino-substituted triphenylamine derivatives. J Electroanal Chem 575:95–101.

  4. 4.

    Yen HJ, Guo SM, Liou GS (2010) Synthesis and unexpected electrochemical behavior of the triphenylamine-based aramids with ortho-and Para-trimethyl-protective substituents. J Polym Sci A Polym Chem 48:5271–5281.

  5. 5.

    Wang HM, Hsiao SH (2009) Electrochemically and electrochromically stable polyimides bearing tert-butyl-blocked N, N, N′,N′-tetraphenyl-1, 4-phenylenediamine units. Polymer 50:1692–1699.

  6. 6.

    Hsiao SH, Liao WK, Liou GS (2017) Synthesis and electrochromism of highly organosoluble polyamides and polyimides with bulky trityl-substituted triphenylamine units. Polymers 9:511.

  7. 7.

    Lee MJ, Kwak YJ, Seok WC, Lee SW (2016) Synthesis, characterization and electrochromic properties of polyamides having triphenylamine derivatives. Polym Bull 73:2427–2438.

  8. 8.

    Khalid N, Park OO, Akhter T, Siddiqi HM (2017)) Fluorescent, electroactive, thermally stable triphenylamine-and naphthalene-based polyimides for optoelectronic applications. Journal of Applied Polymer Science 134:44526.

  9. 9.

    Liou GS, Hsiao SH, Ishida M, Kakimoto M, Imai Y (2002) Synthesis and characterization of novel soluble triphenylamine-containing aromatic polyamides based on N, N′-bis (4-aminophenyl)-N,N′-diphenyl-1, 4-phenylenediamine. J Polym Sci A Polym Chem 40:2810–2818.

  10. 10.

    Yen HJ, Liou GS (2012) Solution-processable triarylamine-based electroactive high performance polymers for anodically electrochromic applications, polymer chemistry 2:255-264.DOI.

  11. 11.

    Debaditya B, Bandyopadhyay P, Ghosh S, Banerjee S, Padmanabhan (2015) Highly gas permeable aromatic polyamides containing adamantane substituted triphenylamine. J Membr Sci 474:20–31.

  12. 12.

    Ningwei S, Su K, Zhou Z, Yu Y, Tian X, Wang D, Zhao X, Zhou H, Chen C (2018) AIE-active polyamide containing diphenylamine-TPE moiety with superior electrofluorochromic performance, ACS applied materials & interfaces 10:16105-16112.DOI.

  13. 13.

    Yuan WZ, Lu P, Chen S, Lam JW, Wang Z, Liu Y, Kwok HS, Ma Y, Tang BZ (2010) Changing the behavior of chromophores from aggregation-caused quenching to aggregation-induced emission: development of highly efficient light emitters in the solid state. Advanced Materials 22:2159–2163.

  14. 14.

    Yanqiu W, Liang Y, Zhu J, Bai X, Jiang X, Zhang Q, Niu H (2015) High coloration efficiency and fast switching speed of poly (amic acid-imide) s containing triphenylamine in acidic electrolyte. RSC Adv 5:11071–11076.

  15. 15.

    Liou GS, Lin KH (2009) Synthesis and characterization of a novel electrochromic aromatic polyamide from AB-type triphenylamine-based monomer. J Polym Sci A Polym Chem 47:1988–2001.

  16. 16.

    Chang CW, Liou GS, Hsiao SH (2007) Highly stable anodic green electrochromic aromatic polyamides: synthesis and electrochromic properties. J Mater Chem 17:1007–1015.

  17. 17.

    Chattopadhyay DK, Webster DC (2009) Thermal stability and flame retardancy of polyurethanes. Prog Polym Sci 34:1068–1133.

  18. 18.

    Guardia L, Mark J, Hale RC, Harvey E (2006) Detailed polybrominated diphenyl ether (PBDE) congener composition of the widely used penta-, octa-, and deca-PBDE technical flame-retardant mixtures. Environ Sci Technol 40:6247–6254.

  19. 19.

    Hsiao SH, Liou GS, Kung YC, Hsiung TJ (2010) Synthesis and properties of new aromatic polyamides with redox-active 2, 4-dimethoxytriphenylamine moieties. J Polym Sci A Polym Chem 48:3392–3401.

  20. 20.

    Jiwei C, Niu H, Wang C, Ma L, Bai X, Wang W (2012) Tuning the bandgaps of polyazomethines containing triphenylamine by different linkage sites of dialdhyde monomers. Electrochim Acta 76:229–241.

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Declaration of interest

Financial support of this project was provided by the Higher education Commission of Pakistan under the National Research Program for Universities research project 20–3821/NRPU/R&D/HEC/14.

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Correspondence to Humaira Masood Siddiqi.

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Khalid, N., Shumail, S., Siddiqi, H.M. et al. Triphenylamine based redox-active, fluorescent polyamides: synthesis and photophysics. J Polym Res 27, 51 (2020).

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  • Redox-active
  • Blue light emission
  • Electroactive polyamides
  • Fluorescence
  • Triphenylamine polyamide