Triazine-containing blue emitting Hyperbranched polyamide with donor-acceptor architecture: synthesis, characterization, optoelectronic properties, and sensing behaviors toward ferric ions

  • Xiaobing Hu
  • Yaning Guo
  • Dongmei Wang
  • Xiaohua Pu
  • Qiang Chen


Two novel blue-emitting triazine-containing hyperbranched amides with donor-acceptor architecture were designed and synthesized via a one-pot polycondensation using 2,4,6-tris(4-carboxyphenyl)-1,3,5-triazine (H3TATB) and p-phenylenediamine as reaction materials. The prepared polymers were characterized using fourier transform infrared spectroscopy (FTIR), 1H–nuclear magnetic resonance (1H–NMR), and gel permeation chromatography (GPC) analyses. The two polymers are almost amorphous and are soluble in DMSO. Their solutions mainly emitted strong blue light (457–476 nm). The fluorescence quantum yields (QYs) in DMSO were calculated as 41% and 8% for P1–1 and P2–1, respectively. Density functional theory (DFT) calculations demonstrated that the highest occupied molecular orbit (HOMO) and lowest unoccupied molecular orbit (LUMO) were effectively separated with p-phenylenediamine as a donor unit and H3TATB as an acceptor unit. The effective HOMO−LUMO separation helps to induce intramolecular charge transfer from the HOMO to the LUMO. This results a relatively small energy gap between the singlet and triplet excited states, and as a consequence, these polymers are expected to harness both singlet and triplet excitons for light emission, leading to high external electroluminescence efficiency. The merits of the two polymers are organo-solubility and high fluorescence quantum yield. Both P1–1 and P2–1 are sensitive fluorescent indicators for Fe3+ ion. They are potential useful in the area of blue light emitting, display and fluorescent chemosensor for Fe3+ ion.


hyperbranched polyamide 2,4,6-tris(4-carboxyphenyl)-1,3,5-triazine fluorescence quantum yield donor-acceptor architecture fluorescent chemosensor 



The author thanks the Scientific research project fund of Shaanxi Province Key Laboratory of Phytochemistry of China (14JS006), the Doctoral research start-up project fund of Baoji University of Arts and Sciences (ZK2017032), the Nature science project fund of Shaanxi Educational Committee of China (16JK1050) and the project fund of Baoji University of Arts and Sciences (ZK15049) for the support.

Supplementary material

10965_2018_1456_MOESM1_ESM.docx (6.4 mb)
ESM 1 (DOCX 6.39 mb)


  1. 1.
    Zhong Z, Zhao S, Pei J, Wang J, Ying L, Peng J, Cao Y (2016) An alkane-soluble dendrimer as electron-transport layer in polymer light-emitting diodes. ACS Appl Mater Inter 8:20237–20242. CrossRefGoogle Scholar
  2. 2.
    Sun J, Wang H, Yang T, Zhang X, Li J, Zhang T, Wu Y, Chen W, Wong W-Y, Xu B (2016) Design, synthesis and properties of triple-color hyperbranched polymers derived from poly(9,9-dioctylfluorene) with phosphorescent core tris(1-phenylisoquinoline)iridium(III). Dyes Pigments 125:339–347. CrossRefGoogle Scholar
  3. 3.
    Shizu K, Noda H, Tanaka H, Taneda M, Uejima M, Sato T, Tanaka K, Kaji H, Adachi C (2015) Highly efficient blue electroluminescence using delayed-fluorescence emitters with large overlap density between luminescent and ground states. J Phys Chem C 119:26283–26289. CrossRefGoogle Scholar
  4. 4.
    Forrest SR (2004) The path to ubiquitous and low-cost organic electronic appliances on plastic. Nature 428:911–918. CrossRefGoogle Scholar
  5. 5.
    Reineke S, Thomschke M, Lüssem B, Leo K (2013) White organic light-emitting diodes: status and perspective. Rev Mod Phys 85:1245–1293. CrossRefGoogle Scholar
  6. 6.
    Zhu L, Yang C, Zhong C, Xu L, Qin J (2008) Novel fluorene-based copolymer with pendant aza-crown ether: highly sensitive and specific detection for CuSO4 and concurrent effect of anions. Polymer 49:3716–3721. CrossRefGoogle Scholar
  7. 7.
    Guo T, Yu L, Zhao B, Li Y, Tao Y, Yang W, Hou Q, Wu H, Cao Y (2012) Highly efficient, red-emitting Hyperbranched polymers utilizing a phenyl-Isoquinoline iridium complex as the Core. Macromol Chem Phys 213:820–828. CrossRefGoogle Scholar
  8. 8.
    Wu HB, Zou JH, Liu F, Wang L, Mikhailovsky A, Bazan GC, Yang W, Cao Y (2008) Efficient single active layer Electrophosphorescent white polymer light-emitting diodes. Adv Mater 20:696–702. CrossRefGoogle Scholar
  9. 9.
    Wu Y, Hao X, Wu J, Jin J, Ba X (2010) Pure blue-light-emitting materials: Hyperbranched ladder-type poly(p-phenylene)s containing Truxene units. Macromolecules 43:731–738. CrossRefGoogle Scholar
  10. 10.
    Chen J, Peng H, Law CCW, Dong Y, Lam JWY, Williams ID, Tang BZ (2003) Hyperbranched poly(phenylenesilolene)s: synthesis, thermal stability, electronic conjugation, optical power limiting, and cooling-enhanced light emission. Macromolecules 36:4319–4327. CrossRefGoogle Scholar
  11. 11.
    Li J, Bo ZS (2004) “AB2+AB” approach to Hyperbranched polymers used as polymer blue light emitting materials. Macromolecules 37:2013–2015. CrossRefGoogle Scholar
  12. 12.
    Xin Y, Wen G, Zeng W, Zhao L, Zhu X, Fan Q, Feng J, Wang L, Wei B, Cao Y, Huang W (2005) Hyperbranched Oxadiazole-containing Polyfluorenes: toward stable blue light PLEDs. Macromolecules 38:6755–6758. CrossRefGoogle Scholar
  13. 13.
    Wang PW, Liu YJ, Devadoss C, Bharathi P, Moore JS (1996) Electroluminescent diodes from a single component emitting layer of dendritic macromolecules. Adv Mater 8:237–241. CrossRefGoogle Scholar
  14. 14.
    Vanjinathan M, Lin HC, Nasar AS (2012) Design, synthesis, photophysical, and electrochemical properties of DCM-based conjugated polymers for light-emitting devices. J Polym Sci A Polym Chem 50:3806–3818. CrossRefGoogle Scholar
  15. 15.
    Zeng SM, Ouyang XH, Zeng HP, Ji W, Ge ZY (2012) Synthesis, tunable two and three-photon absorption properties of triazine derivatives by branches. Dyes Pigments 94:290–295. CrossRefGoogle Scholar
  16. 16.
    Li XM, Zhang J, Huang GL, Wang YF, Rong MZ, Teng MY, Liu J (2017) A bipolar thiophene substituted 1,3,5-triazine host material for green phosphorescent OLEDs with low onset voltage and current efficiency roll-off. Dyes Pigments 141:1–4. CrossRefGoogle Scholar
  17. 17.
    Elim HI, Anandakathir R, Jakubiak R, Chiang LY, Ji W, Tan LS (2007) Large concentration-dependent nonlinear optical responses of starburst diphenylaminofluorenocarbonyl methano[60]fullerene pentads. J Mater Chem 17:1826–1838. CrossRefGoogle Scholar
  18. 18.
    Wang HL, Li Z, Shao P, Qin JG, Huang ZL (2010) Two-photon absorption property of a conjugated polymer: influence of solvent and concentration on its property. J Phys Chem B 114:22–27. CrossRefGoogle Scholar
  19. 19.
    Matsushima T, Takamori M, Miyashita Y, Honma Y, Tanaka T, Aihara H, murata H (2010) High electron mobility layers of triazines for improving driving voltages, power conversion efficiencies, and operational stability of organic light-emitting diodes. Org Electron 11:16–22. CrossRefGoogle Scholar
  20. 20.
    Butchosa C, McDonald TO, Cooper AI, Adams DJ, Zwijnenburg MA (2014) Shining a light on s-Triazine-based polymers. J Phys Chem C 118:4314–4324. CrossRefGoogle Scholar
  21. 21.
    Wagner D, Hoffmann ST, Heinemeyer U, Munster I, Kohler A, Strohriegl P (2013) Triazine based bipolar host materials for blue phosphorescent OLEDs. Chem Mater 25:3758–3765. CrossRefGoogle Scholar
  22. 22.
    Wang Q, Wallace JU, Lee TYH, Ou JJ, Tsai YT, Huang YH, Wu CC, Rothberg LJ, Chen SH (2013) Evaluation of propylene-, meta-, and para-linked triazine and tert-butyltriphenylamine as bipolar hosts for phosphorescent organic light-emitting diodes. J Mater Chem C 1:2224–2232. CrossRefGoogle Scholar
  23. 23.
    Su SJ, Cai C, Takamatsu J, Kido J (2012) A host material with a small singlet–triplet exchange energy for phosphorescent organic light-emitting diodes: guest, host, and exciplex emission. Org Electron 13:1937–1947. CrossRefGoogle Scholar
  24. 24.
    Liu XK, Zheng CJ, Xiao J, Ye J, Liu CL, Wang SD, Zhao WM, Zhang XH (2012) Novel bipolar host materials based on 1,3,5-triazine derivatives for highly efficient phosphorescent OLEDs with extremely low efficiency roll-off. Phys Chem Chem Phys 14:14255–14261. CrossRefGoogle Scholar
  25. 25.
    Chang CH, Kuo MC, Lin WC, Chen YT, Wong KT, Chou SH, Ejabul M, Raymond CK, Sean X, Tetsuya N, Chihaya A (2012) A dicarbazole–triazine hybrid bipolar host material for highly efficient green phosphorescent OLEDs. J Mater Chem 22:3832. CrossRefGoogle Scholar
  26. 26.
    Rothmann MM, Haneder S, Como ED, Lennartz C, Schildknecht C, Strohriegl P (2010) Donor-substituted 1,3,5-Triazines as host materials for blue phosphorescent organic light-emitting diodes. Chem Mater 22:2403–2410. CrossRefGoogle Scholar
  27. 27.
    Chen HF, Yang SJ, Tsai ZH, Hung WY, Wang TC, Wong KT (2009) 1,3,5-Triazine derivatives as new electron transport–type host materials for highly efficient green phosphorescent OLEDs. J Mater Chem 19:8112–8118. CrossRefGoogle Scholar
  28. 28.
    Sathiyan G, Sakthivel P (2016) A multibranched carbazole linked triazine based fluorescent molecule for the selective detection of picric acid. RSC Adv 6:106705–106715. CrossRefGoogle Scholar
  29. 29.
    Sathiyan G, Sakthivel P (2017) Synthesis and characterization of triazine linked carbazole derivatives green-light-emitting molecules. Dyes Pigments 143:444–454. CrossRefGoogle Scholar
  30. 30.
    Wada Y, Shizu K, Kubo S, Suzuki K, Tanaka H, Adachi C, Kaji H (2015) Highly efficient electroluminescence from a solution-processable thermally activated delayed fluorescence emitter. Appl Phys Lett 107:183303. CrossRefGoogle Scholar
  31. 31.
    Sun JW, Baek JY, Kim KH, Moon CK, Lee JH, Kwon SK, Kim YH, Kim JJ (2015) Thermally activated delayed fluorescence from Azasiline based intramolecular charge-transfer emitter (DTPDDA) and a highly efficient blue light emitting diode. Chem Mater 27:6675–6681. CrossRefGoogle Scholar
  32. 32.
    Albrecht K, Matsuoka K, Fujita K, Yamamoto K (2015) Carbazole dendrimers as solution-Processable thermally activated delayed-fluorescence materials. Angew Chem Int Ed 54:5677–5682. CrossRefGoogle Scholar
  33. 33.
    Huang B, Yin ZH, Ban XX, Jiang W, Dai Y, Zhang JY, Liu YY, Yang YP, Sun YM (2015) Thermally activated delayed fluorescence of N-phenylcarbazole and triphenylamine functionalised tris(aryl)triazines. Dyes Pigments 117:141–148. CrossRefGoogle Scholar
  34. 34.
    Li YC, Liu JY, Zhao YD, Cao YC (2017) Recent advancements of high efficient donor–acceptor type blue small molecule applied for OLEDs. Mater Today 20:258–266. CrossRefGoogle Scholar
  35. 35.
    Corrochano DR, Hoz ADL, Sánchez-Migallón AM, Caballero R, Ramírez JR (2016) Synthesis of imine-derived triazines with donor–acceptor properties. J Clean Prod 118:223–228. CrossRefGoogle Scholar
  36. 36.
    Dutta T, Woody KB, Parkin SR, Watson MD, Gierschner J (2009) Conjugated polymers with large effective stokes shift: Benzobisdioxole-based poly(phenylene ethynylene)s. J Am Chem Soc 131:17321–17327. CrossRefGoogle Scholar
  37. 37.
    Yan YL, Zhao YS (2014) Organic nanophotonics: from controllable assembly of functional molecules to low-dimensional materials with desired photonic properties. Chem Soc Rev 43:4325–4340. CrossRefGoogle Scholar
  38. 38.
    Liu R, Shu ML, Hu JY, Zhu SQ, Shi H, Zhu HJ (2017) Star-shaped D-π-a compounds with a 1,3,5-triazine core and N-aryl chromophore substituted fluorene arms: synthesis, aggregation induced emission and two-photon absorption. Dyes Pigments 137:174–181. CrossRefGoogle Scholar
  39. 39.
    Do K, Choi H, Lim K, Jo H, Cho JW, Nazeeruddin MK, Ko J (2014) Star-shaped hole transporting materials with a triazine unit for efficient perovskite solar cells. Chem Commun 50:10971–10974. CrossRefGoogle Scholar
  40. 40.
    Quesada M, Pena-O'Shea VADL, Aromi G, Geremia S, Massera C, Roubeau O, Gamez P, Reedijk J (2007) A molecule-based Nanoporous material showing Tuneable spin-crossover behavior near room temperature. Adv Mater 19:1397–1402. CrossRefGoogle Scholar
  41. 41.
    Volz D, Wallesch M, Flechon C, Danz M, Verma A, Navarro JM, Zink DM, Bräse S, Baumann T (2015) From iridium and platinum to copper and carbon: new avenues for more sustainability in organic light-emitting diodes. Green Chem 17:1988–2011. CrossRefGoogle Scholar
  42. 42.
    Dong QC, Tai FF, Lian H, Chen Z, Hu MM, Huang JH, Wong W-Y (2017) Thermally stable bipolar host materials for high efficiency phosphorescent green and blue organic light-emitting diodes. Dyes Pigments 143:470–478. CrossRefGoogle Scholar
  43. 43.
    Balasaravanan R, Duraimurugan K, Sivamani J, Thiagarajan V, Siva A (2015) Synthesis and photophysical properties of triphenylamine-based multiply conjugated star-like molecules. New J Chem 39:7472–7480. CrossRefGoogle Scholar
  44. 44.
    Hua B, Gao Y, Ying S, Liu W, Xue S, Yang W (2015) Synthesis and optoelectronic properties of a solution-processed red-emitting tetra(arylvinyl)anthracene cruciform. Dyes Pigments 123:26–31. CrossRefGoogle Scholar
  45. 45.
    Park J, Feng DW, Zhou H-C (2015) Dual exchange in PCN-333: a facile strategy to chemically robust mesoporous chromium metal–organic framework with functional groups. J Am Chem Soc 137:11801–11809. CrossRefGoogle Scholar
  46. 46.
    Zhang QS, Kuwabara H, Potscavage Jr WJ, Huang SP, Hatae Y, Shibata T, Adachi C (2014) Anthraquinone-based intramolecular charge-transfer compounds: computational molecular design, thermally activated delayed fluorescence, and highly efficient red electroluminescence. J Am Chem Soc 136:18070–18081. CrossRefGoogle Scholar
  47. 47.
    Hawker CJ, Lee R, Fréchet JMJ (1991) One-step synthesis of hyperbranched dendritic polyesters. J Am Chem Soc 113:4583–4588. CrossRefGoogle Scholar
  48. 48.
    Hu XB (2017) 4. Novel fluorescent porous hyperbranched aromatic polyamide containing 1,3,5-triphenylbenzene moieties: synthesis and characterization. J Appl Polym Sci 134.
  49. 49.
    Liu JZ, Zhong YC, Lu P, Hong YN, Lam JWY, Faisal M, Yu Y, Wong KS, Tang BZ (2010) A superamplification effect in the detection of explosives by a fluorescent hyperbranched poly(silylenephenylene) with aggregation-enhanced emission characteristics. Polym Chem 1:426–429. CrossRefGoogle Scholar
  50. 50.
    Chen B, Zhang H, Luo WW, Nie H, Hu RRQAJ, Zhao ZJ, Tang BZ (2017) Oxidation-enhanced emission: exploring novel AIEgens from thieno[3,2-b]thiophene S,S-dioxide. J Mater Chem C 5:960–968. CrossRefGoogle Scholar
  51. 51.
    Chen B, Nie H, Hu R, Qin A, Zhao Z, Tang BZ (2016) Insights into the correlation between the molecular conformational change and AIE activity of 2,5-bis(dimesitylboryl)-3,4-diphenylsiloles. J Mater Chem C 4:7541–7545. CrossRefGoogle Scholar
  52. 52.
    Hu J, Zhang C-Y (2013) Simple and accurate quantification of quantum yield at the single-molecule/particle level. Anal Chem 85:2000–2004. CrossRefGoogle Scholar
  53. 53.
    Melhuish WH (1961) Quantum efficiencies of fluorescence of organic substances: effect of solvent and concentration of the fluorescent solute. J Phys Chem 65:229–235. CrossRefGoogle Scholar
  54. 54.
    Song Y, Yao HY, Tan HW, Zhu SY, Dong B, Guan SW (2017) Changing the memory behaviors from volatile to nonvolatile via end-capping of hyperbranched polyimides with polycyclic arenes. Dyes Pigments 139:730–736. CrossRefGoogle Scholar
  55. 55.
    Uoyama H, Goushi K, Shizu K, Nomura H, Adachi C (2012) Highly efficient organic light-emitting diodes from delayed fluorescence. Nature 492:234–238. CrossRefGoogle Scholar
  56. 56.
    Endo A, Sato K, Yoshimura K, Kai T, Kawada A, Miyazaki H, Adachi C (2011) Efficient up-conversion of triplet excitons into a singlet state and its application for organic light emitting diodes. Appl Phys Lett 98:083302. CrossRefGoogle Scholar
  57. 57.
    Özcan E, Tümay SO, Alidağı HA, Çoşut B, Yeşilot S (2016) A new cyclotriphosphazene appended phenanthroline derivative as a highly selective and sensitive OFF–ON fluorescent chemosensor for Al3+ ions. Dyes Pigments 132:230–236. CrossRefGoogle Scholar
  58. 58.
    Antina EV, Bumagina NA, V'yugin AI, Solomonov AV (2017) Fluorescent indicators of metal ions based on dipyrrоmethene platform. Dyes Pigments 136:368–381. CrossRefGoogle Scholar
  59. 59.
    Gupta VK, Singh AK, Kumawat LK (2014) Thiazole Schiff base turn-on fluorescent chemosensor for Al3+ ion. Sensors Actuators B Chem 195:98–108. CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media B.V., part of Springer Nature 2018

Authors and Affiliations

  1. 1.College of Chemistry and Chemical EngineeringBaoji University of Arts and SciencesBaojiPeople’s Republic of China

Personalised recommendations