Skip to main content
SpringerLink
Log in

Synthesis of 4-(5-bromo) pyridinyl pyrazolinone derivatives and the modulation of their photoresponsive properties

  • Published:
Journal of Materials Science: Materials in Electronics Aims and scope Submit manuscript

Abstract

Pyrazolinone derivatives are a new class of organic photochromic materials with excellent optical color change properties in the powder crystal state, which show great potential for applications, including high-density storage, fluorescence switching, and bioimaging. Their design and synthesis with structural photoreversibility and excellent fluorescence modulation properties are areas of research focus. Rational modification of the molecular backbone with the introduction of the 5-bromopyridine group at the 4-position of the pyrazolinone ring was used to prepare three pyrazolinone condensed aminothiourea derivatives with photoreversible color change in the powder crystal state. The molecular structures of the compounds were confirmed by mass spectrometry and nuclear magnetic resonance spectroscopy. The changes in the infrared spectra indicated alcoholic to ketonic transformation in the molecular structures upon ultraviolet (UV) illumination. The ultraviolet-visible (UV–vis) absorption spectra showed significant photoreversible changes in all three derivatives, and the introduction of the electron-absorbing phenyl group resulted in the most significant fading of DP5Br3PyBP-PTSC. The fluorescence emission spectra showed that the three derivatives have prominent blue fluorescence. Their fluorescence emission intensity gradually decreased until the increase in UV illumination time produced quenching. The property of excellent fluorescence reversibility under the alternating UV and visible light was shown by all three derivatives, which are expected to be applied in fluorescent molecular switches.

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

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9

Similar content being viewed by others

Data availability

The authors declare that the data are available within the article.

References

  1. T.J. Kucharski, Y.C. Tian, S. Akbulatov, R. Boulatov, Chemical solutions for the closed-cycle storage of solar energy. Energy Environ. Sci. 4, 4449–4472 (2011)

    Article  CAS  Google Scholar 

  2. A.S. Bhavna, R.S. Pratima, V.S. Surati, Chemionics study of newly synthesized photochromic schiff base compound. Mol. Cryst. Liq. Cryst 575, 115–127 (2013)

    Article  Google Scholar 

  3. H. Dridi, A. Boulmier, P. Bolle, A. Dolbecq, J.N. Rebilly, F. Banse, L. Ruhlmann, B. Serier, R. Dessapt, P. Mialane, Directing the solid-state photochromic and luminescent behaviors of spiromolecules with Dawson and Anderson polyoxometalate units. J. Mater. Chem. C 8, 637–649 (2020)

    Article  CAS  Google Scholar 

  4. S.L. Li, M. Han, Y. Zhang, G.P. Li, M. Li, G. He, X.M. Zhang, X-Ray and UV dual photochromism, thermochromism, electrochromism, and amine-selective chemochromism in an Anderson-like Zn7 cluster-based 7-fold interpenetrated framework. J. Am. Chem. Soc. 141, 12663–12672 (2019)

    Article  CAS  Google Scholar 

  5. G. Pariani, R. Castagna, G. Dassa, S. Hermes, C. Vailati, A. Bianco, C. Bertarelli, Diarylethene-based photochromic polyurethanes for multistate optical memories. J. Mater. Chem. 21, 13223–13231 (2011)

    Article  CAS  Google Scholar 

  6. Y. Nakamichi, Y. Hirai, H. Yabu, M. Shimomura, Fabrication of patterned and anisotropic porous films based on photo-cross-linking of poly(1,2-butadiene) honeycomb films. J. Mater. Chem. 21, 3884–3889 (2011)

    Article  CAS  Google Scholar 

  7. M. Taguchi, T. Nakagawa, T. Nakashima, T. Kawai, Photochromic and fluorescence switching properties of oxidized triangle terarylenes in solution and in amorphous solid states. J. Mater. Chem. 21, 17425–17432 (2011)

    Article  CAS  Google Scholar 

  8. H. Jiang, C. Sun, C.M. Yu, M.S. Wang, G.C. Guo, Broadband photoresponsive bismuth halide hybrid semiconductors built with π-stacked photoactive polycyclic viologen. Inorg. Chem. 60, 5538–5544 (2021)

    Article  CAS  Google Scholar 

  9. I. Yildiz, E. Deniz, F.M. Raymo, Fluorescence modulation with photochromic switches in nanostructured constructs. Chem. Soc. Rev. 38, 1859–1867 (2009)

    Article  CAS  Google Scholar 

  10. X.D. Huang, G.H. Wen, S.S. Bao, J.G. Jia, L.M. Zheng, Thermo- and light-triggered reversible interconversion of dysprosium anthracene complexes and their responsive optical, magnetic and dielectric properties. Chem. Sci. 12, 929–937 (2021)

    Article  CAS  Google Scholar 

  11. M. Heilemann, P. Dedecker, J. Hofkens, M. Sauer, Photoswitches: key molecules for subdiffraction-resolution fluorescence imaging and molecular quantification. Laser. Photon. Rev. 3, 180–202 (2009)

    Article  CAS  Google Scholar 

  12. H.K. Yang, A.E. Ozcam, K. Efimenko, J. Genzer, Photochromic materials with tunable color and mechanical flexibility. Soft. Matter 7, 3766–3774 (2011)

    Article  CAS  Google Scholar 

  13. D. Ramachandran, F. Liu, M.W. Urban, Self-repairable copolymers that change color. RSC Adv. 2, 135–143 (2012)

    Article  CAS  Google Scholar 

  14. S.D. Han, J.X. Hu, G.M. Wang, Recent advances in crystalline hybrid photochromic materials driven by electron transfer. Coord. Chem. Rev. 452, 214304 (2022)

    Article  CAS  Google Scholar 

  15. C. Sanchez, K.J. Shea, S. Kitagawa, Hybrid materials themed issue. Chem. Soc. Rev. 40, 672–687 (2011)

    Google Scholar 

  16. Q. Zhang, J. Hu, Q. Li, D. Feng, Z. Gao, G. Wang, Single molecule magnetic behavior and photo-enhanced proton conductivity in a series of photochromic complexes. Chin. Chem. Lett. 33, 1417–1421 (2022)

    Article  CAS  Google Scholar 

  17. M. Hu, S. Kawauchi, M. Satoh, Two-photon photochromism of two simple chromene derivatives. J. Photochem. Photobiol. A 150, 131–141 (2002)

    Article  CAS  Google Scholar 

  18. R.S. Pratima, A.S. Bhavna, Photochromic and molecular switching behaviour of schiff base-containing pyrazolone ring. Chem. Pap. 69, 368–375 (2015)

    Google Scholar 

  19. X. Huang, T. Li, Recent progress in the development of molecular-scale electronics based on photoswitchable molecules. J. Mater. Chem. C 8, 821–848 (2020)

    Article  CAS  Google Scholar 

  20. S.A. Abdulrahman, M.A. Reda, A.A. Nawaa, M.E. Khaled, Synthesis, chemical reactivities, and biological properties of pyrazolone/pyrazolinone as a blocking unit for building various heterobicyclic systems: a review. Mini-Rev. Org. Chem 18, 220–235 (2021)

    Google Scholar 

  21. S.C. Peng, J.H. Wen, M.T. Hai, Z. Yang, X.T. Yuan, D. Wang, H. Cao, W.L. He, Synthesis and application of reversible fluorescent photochromic molecules based on tetraphenylethylene and photochromic groups. New. J. Chem. 43, 617–621 (2019)

    Article  CAS  Google Scholar 

  22. J.X. Wang, C. Li, H. Tian, Energy manipulation and metal assisted photochromism in photochromic metal complex. Coord. Chem. Rev. 427, 213579 (2021)

    Article  CAS  Google Scholar 

  23. N.S. Menez, V. Monnier, I. Colombier, P.L. Baldeck, M. Irie, A. Ibanez, Photochromic fluorescent diarylethene nanocrystals grown in sol-gel thin films. Dyes Pigm. 89, 241–245 (2011)

    Article  Google Scholar 

  24. T. Köpplmayr, M. Cardinale, G. Jakopic, G. Trimmel, W. Kern, T. Griesser, Photosensitive polymers bearing fully aromatic esters for multilayer data storage devices. J. Mater. Chem. 21, 2965–2973 (2011)

    Article  Google Scholar 

  25. Z.S. Lu, Y.S. Liu, W.H. Hu, X.W. Lou, C.M. Li, Rewritable multicolor fluorescent patterns for multistate memory devices with high data storage capacity. Chem. Comm. 47, 9609–9611 (2011)

    Article  CAS  Google Scholar 

  26. Q. Li, Q. Zhang, W.J. Wei, A.N. Wang, J.X. Hu, G.M. Wang, Light actuated stable radicals of the 9-anthracene carboxylic acid for designing new photochromic complexes. Chem. Commun. 57, 4295–4298 (2021)

    Article  CAS  Google Scholar 

  27. A. Shylaja, S.R. Rubina, S.S. Roja, R.R. Kumar, Novel blue emissive dimethylfuran tethered 2-aminopyridine-3-carbonitrile as dual responsive fluorescent chemosensor for Fe3+ and picric acid in nanomolar detection limit. Dyes Pigm. 174, 108062 (2020)

    Article  CAS  Google Scholar 

  28. I. Kahle, O. Tröber, S. Trentsch, H. Richter, B. Grunler, S. Hemeltjen, M. Schlesinger, M. Mehring, S. Spange, Functional mesoporous aluminosilicate nanoparticles as host material to fabricate photo-switchable polymer films. J. Mater. Chem. 21, 5083–5088 (2011)

    Article  CAS  Google Scholar 

  29. S.Z. Pu, G. Liu, R.J. Wang, B. Chen, Modulation of a fluorescence switch based on a photochromic diarylethene and a rhodamine B dye. Dyes Pigm. 98, 238–245 (2013)

    Article  CAS  Google Scholar 

  30. H.Y. Jung, S. You, C. Lee, S. You, Y. Kim, One-pot synthesis of monodispersed silica nanoparticles for diarylethene-based reversible fluorescence photoswitching in living cells. Chem. Commun. 49, 7528–7530 (2013)

    Article  CAS  Google Scholar 

  31. S.C. Pang, H. Hyun, S. Lee, D. Jang, M.J. Lee, S.H. Kang, K.H. Ahn, Photoswitchable fluorescent diarylethene in a turn-on mode for live cell imaging. Chem. Commun. 48, 3745–3747 (2012)

    Article  CAS  Google Scholar 

  32. Z.M. Virag, O. Oliver, C. Antal, K. Veronika, F. David, S. Pal, Ferrocenyl pyrazolines: preparation, structure, redox properties and DFT study on regioselective ring-closure. J Organomet. Chem. 694, 4185–4195 (2009)

    Article  Google Scholar 

  33. M. Faisal, A. Saeed, S. Hussain, P. Dar, F.A. Larik, Recent developments in synthetic chemistry and biological activities of pyrazole derivatives. J. Chem. Sci. 131, 1–30 (2019)

    Article  CAS  Google Scholar 

  34. F. Tok, B.I. Abas, O. Cevik, B.K. Kaymakcıoglu, Design, synthesis and biological evaluation of some new 2-pyrazoline derivatives as potential anticancer agents. Bioorg. Chem. 102, 104063 (2020)

    Article  CAS  Google Scholar 

  35. B.H. Peng, G.F. Liu, L. Liu, D.Z. Jia, Studies on solid-state proton transfer along hydrogen bond of pyrazolone-ring. Tetrahedron 61, 5926–5932 (2005)

    Article  CAS  Google Scholar 

  36. H. Chai, G.F. Liu, L. Liu, D.Z. Jia, Synthesis and spectroscopic study on photochromism of a new thiosemicarbazone compound containing pyrazolone. Spectrochim. Acta Part A 61, 2590–2594 (2005)

    Article  Google Scholar 

  37. N. Swarnagowri, P. Vinay, H. Gangadhar, K.S. Pai, K.S. Rajeev, N.K. Lokanathe, R. Sri, L.G. Santosh, Synthesis, crystal structure, biological evaluation, DFT calculations and third order nonlinear optical studies of pyrazolines. J. Mol. Struct. 1243, 130780 (2021)

    Article  Google Scholar 

  38. J.X. Guo, D.Z. Jia, L. Liu, H. Yuan, M.X. Guo, D.L. Wu, F. Li, Photochromism and mechanism of pyrazolones in crystals: structural variations directly observed by X-ray diffraction. J. Mater. Chem. 21, 12202–12205 (2011)

    Article  CAS  Google Scholar 

  39. S. Adam, H. Karolina, M. Andrzej, M. Jaroslaw, Photoinduced birefringence in PMMA polymer doped with photoisomerizable pyrazoline derivative. J. Phys. Chem. C 119, 10007–10014 (2015)

    Article  Google Scholar 

  40. B.S. Jenson, The synthesis of 1 Phenyl-3-methyl 4-acl-pyrazolones-5. Acta Chem. Scand. 13, 1668–1670 (1959)

    Article  Google Scholar 

  41. L. Liu, X.Y. Xie, D.Z. Jia, Synthesis and properties of a novel photochromic compound with modulated fluorescence in the solid state. J. Org. Chem. 75, 4742–4747 (2010)

    Article  CAS  Google Scholar 

  42. Y.Y. Che, L. Liu, Y.K. Tang, Y.Q. Qiao, X.M. Zhao, S.S. Gao, S. Ding, D.Z. Jia, Solid-state photochromic behavior of pyrazolone 4-phenylthiosemicarbazones. New. J. Chem. 41, 15229–15235 (2017)

    Article  CAS  Google Scholar 

  43. L.C. Andreea, R. Gheorghe, C. Corneliu, S. Sergiu, S. Gabriela, S. Mihaela, S. Liviu, Bichromophoric pyrazoline derivative with solvent-selective photoluminescence quenching. J. Mol. Liq. 278, 156–163 (2019)

    Article  Google Scholar 

Download references

Funding

The work was financially supported by Kashi Science and Technology Plan Project (KS2022095) and Teaching and Reform Project of Xinjiang Uygur Autonomous Region (PT-2021051).

Author information

Authors and Affiliations

  1. College of Chemistry and Environmental Science, Laboratory of Xinjiang Native Medicinal and Edible Plant Resources Chemistry, Kashi University, Kashi, 844000, China

    Yucai Zhang & Abdulla Yusuf

  2. School of Chemistry and Chemical Engineering, Key Laboratory for Green Processing of Chemical Engineering of Xinjiang Bingtuan, Shihezi University, Shihezi, 832003, China

    Renpan Deng

Authors
  1. Yucai Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Abdulla Yusuf
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Renpan Deng
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

YZ conceived the idea and carried the experimental work. AY provided positive suggestions on our work. Data analysis were done by RD. All authors contributed to the preparation of this paper.

Corresponding author

Correspondence to Yucai Zhang.

Ethics declarations

Competing interests

The authors have not disclosed any competing interests.

Additional information

Publisher’s Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary Information

Below is the link to the electronic supplementary material.

Supplementary material 1 (DOCX 438.0 kb)

Rights and permissions

Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Zhang, Y., Yusuf, A. & Deng, R. Synthesis of 4-(5-bromo) pyridinyl pyrazolinone derivatives and the modulation of their photoresponsive properties. J Mater Sci: Mater Electron 34, 947 (2023). https://doi.org/10.1007/s10854-023-10390-1

Download citation

  • Received:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1007/s10854-023-10390-1

Search

Navigation