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Donor-Pi-Acceptor Fluorene Conjugates, Based on Chalcone and Pyrimidine Derivatives: an Insight into Structure-Property Relationship, Photophysical and Electrochemical Properties

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Abstract

A small set of four new fluorenyl chromophores (5-5a-c) was accomplished by stepwise nucleophilic substitution, Friedel-Crafts acylation, Ullman coupling, aldol condensation and cyclization reactions. The fluorene moiety was substituted at 2,7,9 and 9′ positions with diverse groups. The synthesized derivatives were characterized by FTIR, 1H-NMR and 13C-NMR spectroscopic techniques. The optical properties were evaluated by by UV-VIS absorption and Fluorescence studies. HOMO and LUMO energy levels were evaluated by electrochemical studies and were found at −5.37-5.83 eV and − 2.47-2.94 eV respectively with band gap energy values 2.88 to 2.91 eV. The band gap energy values suggested that these synthesized molecules can be manipulated in the designing of blue and green OLEDS.

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References

  1. Belfield KD, Hagan DJ, Van Stryland EW, Schafer KJ, Negres RA (1999) New two-photon absorbing fluorene derivatives: synthesis and nonlinear optical characterization. Org Lett 1:1575–1578

    Article  CAS  Google Scholar 

  2. Belfield KD, Ren X, Van Stryland EW, Hagan DJ, Dubikovsky V, Miesak EJ (2000) Near-IR two-photon photoinitiated polymerization using a fluorone/amine initiating system. J Am Chem Soc 122:1217–1218

    Article  CAS  Google Scholar 

  3. Belfield KD, Morales AR, Kang BS, Hales JM, Hagan DJ, Van Stryland EW, Chapela VM, Percino J (2004) Synthesis, characterization, and optical properties of new two-photon-absorbing fluorene derivatives. Chem Mater 16:4634–4641

    Article  CAS  Google Scholar 

  4. Belfield KD, Morales AR, Hales JM, Hagan DJ, Van Stryland EW, Chapela VM, Percino J (2004) Linear and two-photon photophysical properties of a series of symmetrical diphenylaminofluorenes. Chem Mater 16:2267–2273

    Article  CAS  Google Scholar 

  5. Hales JM, Hagan DJ, Van Stryland EW, Schafer KJ, Morales AR, Belfield KD, Pacher P, Kwon O, Zojer E, Brédas JL (2004) Resonant enhancement of two-photon absorption in substituted fluorene molecules. J Chem Phys 121:3152–3160

    Article  CAS  Google Scholar 

  6. Belletête M, Beaupré S, Bouchard J, Blondin P, Leclerc M, Durocher G (2000) Theoretical and experimental investigations of the spectroscopic and photophysical properties of fluorene-phenylene and fluorene-thiophene derivatives: precursors of light-emitting polymers. J Phys Chem B 104:9118–9125

    Article  Google Scholar 

  7. Keivanidis PE, Howard IA, Friend RH (2008) Intermolecular interactions of perylene diimides in photovoltaic blends of fluorene copolymers: disorder effects on photophysical properties, film morphology and device efficiency. Adv Funct Mater 18:3189–3202

    Article  CAS  Google Scholar 

  8. Chase DT, Fix AG, Rose BD, Weber CD, Nobusue S, Stockwell CE, Zakharov LN, Lonergan MC, Haley MM (2011) Electron-accepting 6, 12-diethynylindeno [1, 2-b] fluorenes: synthesis, crystal structures, and photophysical properties. Angew Chem Int Ed 50:11103–11106

    Article  CAS  Google Scholar 

  9. Achelle S, Rodríguez-López J, Larbani M, Plaza-Pedroche R, Robin-le Guen F (2019) Carbazole-and triphenylamine-substituted pyrimidines: synthesis and photophysical properties. Molecules 24:1742

  10. Manivarman S, Subashchandrabose S (2017) Molecular properties of the valence isomers of diazines: density functional theory (DFT) and møller plesset (mp2) methods. Karbala Int J Modern Sci 3:18–28

  11. El Aslaoui Z, Karzazi Y (2017) Theoretical investigation of new pyrimidines π-conjugated based materials for photovoltaic applications. J Mater Environ Sci 8:1291–1300

    Google Scholar 

  12. Cheng Y, Shabir G, Li X, Fang L, Xu L, Zhang H, Li E (2020) Development of a deep-red fluorescent glucose-conjugated bioprobe for in vivo tumor targeting. Chem Commun 56:1070–1073

    Article  CAS  Google Scholar 

  13. Lim E, Jung BJ, Lee J, Shim HK, Lee JI, Yang YS, Do LM (2005) Thin-film morphologies and solution-processable field-effect transistor behavior of a fluorene− thieno [3, 2-b] thiophene-based conjugated copolymer. Macromolecules 38:4531–4535

    Article  CAS  Google Scholar 

  14. Tang W, Ke L, Tan L, Lin T, Kietzke T, Chen ZK (2007) Conjugated copolymers based on fluorene− thieno [3, 2-b] thiophene for light-emitting diodes and photovoltaic cells. Macromolecules 40:6164–6171

    Article  CAS  Google Scholar 

  15. Yang L, Feng JK, Ren AM (2005) Theoretical studies on the electronic and optical properties of two thiophene–fluorene based π-conjugated copolymers. Polymer 46:10970–10981

    Article  CAS  Google Scholar 

  16. Pasha MA, Myint YY (2004) Acid-catalysed selective monoiodination of electron-rich arenes by alkali metal iodides. Syn Commun 34:2829–2833

    Article  CAS  Google Scholar 

  17. Bansal RC, Eisenbrown EJ, Ryba RJ (1987) The iodination of fluorene to 2, 7-diiodofluorene. Org Prep Proced Int 19:258–260

    Article  CAS  Google Scholar 

  18. Pond SJ, Tsutsumi O, Rumi M, Kwon O, Zojer E, Brédas JL, Perry JW (2004) Metal-ion sensing fluorophores with large two-photon absorption cross sections: aza-crown ether substituted donor− acceptor− donor distyrylbenzenes. J Am Chem Soc 126:9291–9306

  19. Chiang CL, Wu MF, Dai DC, Wen YS, Wang JK, Chen CT (2005) Red-emitting fluorenes as efficient emitting hosts for non-doped, organic red-light-emitting diodes. Adv Funct Mater 15:231–238

  20. El-Sayed HA, El-Hashash MM, Ahmed AE (2018) Novel synthesis, ring transformation and anticancer activity of 1, 3-thiazine, pyrimidine and triazolo [1, 5-a] pyrimidine derivatives. Bull Chem Soc Ethiopia 32:513–522

    Article  CAS  Google Scholar 

  21. Thomas KRJ, Baheti A (2013) Fluorene based organic dyes for dye sensitised solar cells: structure–property relationships. Mater Tech 28:71–87

    Article  Google Scholar 

  22. De AK, Goswami D (2009) A systematic study on fluorescence enhancement under single-photon pulsed illumination. J Fluoresc 19:931–937

    Article  Google Scholar 

  23. Langhals H, Walter A, Rosenbaum E, Johansson LBA (2011) A versatile standard for bathochromic fluorescence based on intramolecular FRET. Phys Chem Chem Phys 13:11055–11059

    Article  CAS  Google Scholar 

  24. Craig GW (2011) The woodward research institute, robert burns woodward (1917–1979) and chemistry behind the glass door. Helv Chim Acta 94:923–946

  25. Baier MC, Huber J, Mecking S (2009) Fluorescent conjugated polymer nanoparticles by polymerization in miniemulsion. J Am Chem Soc 131:14267–14273

    Article  CAS  Google Scholar 

  26. Benning S, Kitzerow HS, Bock H, Achard MF (2000) Fluorescent columnar liquid crystalline 3, 4, 9, 10-tetra-(n-alkoxycarbonyl)-perylenes. Liq Cryst 27:901–906

    Article  CAS  Google Scholar 

  27. Görl D, Zhang X, Würthner F (2012) Molecular assemblies of perylene bisimide dyes in water. Angew Chem Int Ed 51:6328–6348

    Article  Google Scholar 

  28. Berberich M, Natali M, Spenst P, Chiorboli C, Scandola F, Würthner F (2012) Nondestructive photoluminescence read-out by intramolecular electron transfer in a perylene bisimide-diarylethene dyad. Chem Eur J 18:13651–13664

    Article  CAS  Google Scholar 

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Acknowledgements

We are thankful to PAK-USAID for financial assistance and also thankful to HEC Pakistan for funding.

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Authors and Affiliations

  1. Department of Chemistry, Quaid-i-Azam University, Islamabad, 44000, Pakistan

    Jamaluddin Mahar, Ghulam Shabir, Pervaiz Ali Channar, Aamer Saeed & Madiha Irfan

  2. College of Science and Liberal Arts, New Jersey Institute of Technology, University Heights, NJ, Newark, NJ, 07102, USA

    Kevin D. Belfield

  3. Department of Basic Sciences and Humanities, Khwaja Fareed University of Engineering and Information Technology (KFUEIT), Rahim Yar Khan, 64200, Pakistan

    Madiha Irfan

  4. Center of Engineering Research, KFUPM, Dhahran, 31261, Kingdom of Saudi Arabia

    Anwar Ul-Hamid

Authors
  1. Jamaluddin Mahar
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  2. Ghulam Shabir
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  3. Pervaiz Ali Channar
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  4. Aamer Saeed
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  5. Kevin D. Belfield
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  6. Madiha Irfan
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  7. Anwar Ul-Hamid
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Correspondence to Aamer Saeed.

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Jamaluddin Mahar and Ghulam Shabir both are first authors.

Research Highlights

• Facile synthesis of Pyrimidine derivatives of Fluorene chromophore by multistep strategy.

• Large stokes shift values and high fluorescence quantum yields.

• Chromophores exhibiting oxidation potential.

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Mahar, J., Shabir, G., Channar, P.A. et al. Donor-Pi-Acceptor Fluorene Conjugates, Based on Chalcone and Pyrimidine Derivatives: an Insight into Structure-Property Relationship, Photophysical and Electrochemical Properties. J Fluoresc 30, 419–426 (2020). https://doi.org/10.1007/s10895-020-02516-z

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  • DOI: https://doi.org/10.1007/s10895-020-02516-z

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