Advertisement

Methylated Unsymmetric BODIPY Compounds: Synthesis, High Fluorescence Quantum Yield and Long Fluorescence Time

  • Xian-Fu ZhangEmail author
  • George Q. Zhang
  • Jiale Zhu
ORIGINAL ARTICLE
  • 43 Downloads

Abstract

We show that unsymmetric BODIPY compounds with one, two, and three methyl groups can be synthesized easily and efficiently by the unsymmetric reaction method. Their steady state and time-resolved fluorescence properties are examined in solvents of different polarity. These compounds show high fluorescence quantum yields (0.87 to 1.0), long fluorescence lifetimes (5.89 to 7.40 ns), and small Stokes shift (199 to 443 cm−1). The methyl substitution exhibits influence on the UV-Vis absorption and fluorescence properties, such as the blue shift in emission and absorption spectra. It is the number rather than the position of methyls that play major roles. Except for 3 M-BDP, the increase in the number of methyls on BODIPY core leads to the increase in both fluorescence quantum yield and radiative rate constant, but causes the decrease in fluorescence lifetime. H-bonding solvents increase both the fluorescence lifetime and quantum yields. The methylated BODIPYs show the ability to generate singlet oxygen (1Δg) which is evidenced by near-IR luminescence and DPBF chemical trapping techniques. The formation quantum yield of singlet oxygen (1Δg) for the compounds is up to 0.15 ± 0.05.

Keywords

Unsymmetric BODIPY Fluorescence Synthesis Absorption Methyl substitution 

Notes

Acknowledgements

We thank the financial support from Hebei Provincial Hundred Talents Plan (Contract E2013100005), Hebei Provincial Natural Science Foundation (Contract B2014407080).

Supplementary material

10895_2019_2349_MOESM1_ESM.doc (684 kb)
ESM 1 (DOC 683 kb)

References

  1. 1.
    Kamkaew A, Lim SH, Lee HB, Kiew LV, Chung LY, Burgess K (2013) BODIPY dyes in photodynamic therapy. Chem Soc Rev 42(1):77–88CrossRefGoogle Scholar
  2. 2.
    Boens N, Leen V, Dehaen W (2012) Fluorescent indicators based on BODIPY. Chem Soc Rev 41(3):1130–1172CrossRefGoogle Scholar
  3. 3.
    Ulrich G, Ziessel R, Harriman A (2008) The chemistry of fluorescent bodipy dyes: versatility unsurpassed. Angew Chem Int Ed 47(7):1184–1201CrossRefGoogle Scholar
  4. 4.
    Montalti M, Credi A, Prodi L, Gandolfi MT (2006) Handbook of photochemistry, 3rd edn. Taylor & Francis Group, LLC, Boca RatonGoogle Scholar
  5. 5.
    Kue CS, Ng SY, Voon SH, Kamkaew A, Chung LY, Kiew LV, Lee HB (2018) Recent strategies to improve boron dipyrromethene (BODIPY) for photodynamic cancer therapy: an updated review. Photochem Photobiol Sci Advance Article.  https://doi.org/10.1039/C1038PP00113H
  6. 6.
    Monika Gupta KP, Mula S, Maity DK, Ray AK (2017) Enhanced fluorescence of aqueous BODIPY by interaction with cavitand cucurbit[7]uril. Photochem Photobiol Sci 16:499–506CrossRefGoogle Scholar
  7. 7.
    Reynoso E, Quiroga ED, Agazzi ML, Ballatore MB, Bertolotti SG, Durantini EN (2017) Photodynamic inactivation of microorganisms sensitized by cationic BODIPY derivatives potentiated by potassium iodide. Photochem Photobiol Sci 16:1524–1536CrossRefGoogle Scholar
  8. 8.
    Treibs A, Kreuzer F-H (1968) Difluorboryl-Komplexe von Di- und Tripyrrylmethenen. Eur J Org Chem 718:208–223Google Scholar
  9. 9.
    Arroyo IJ, Hu R, Merino G, Tang BZ, Peña-Cabrera E (2009) The smallest and one of the brightest. Efficient preparation and optical description of the parent Borondipyrromethene system. J Org Chem 74:5719–5722CrossRefGoogle Scholar
  10. 10.
    Schmitt A, Hinkeldey B, Wild M, Jung G (2009) Synthesis of the Core compound of the BODIPY dye class: 4,4′-Difluoro-4-bora-(3a,4a)-diaza-s-indacene. J Fluoresc 19:755–758CrossRefGoogle Scholar
  11. 11.
    Tram K, Yan H, Jenkins HA, Vassiliev S, Bruce D (2009) The synthesis and crystal structure of unsubstituted 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY). Dyes Pigments 82:392–395CrossRefGoogle Scholar
  12. 12.
    Loudet A, Burgess K (2010) BODIPY Dyes and Their Derivatives: Syntheses and spectroscopic properties. In: Kadish K (ed) Handbook of porphyrin science with applications to chemistry, physics, materials science, engineering, biology and medicine, vol 8. World Scientific, Singapore, pp 1–164Google Scholar
  13. 13.
    Palao E, Agarrabeitia AR, Bañuelos-Prieto J, Lopez TA, Ii L-A, Armesto D, Ortiz MJ (2013) 8-functionalization of alkyl-Substituted-3,8-dimethyl BODIPYs by Knoevenagel condensation. Org Lett 15(17):4454–4457CrossRefGoogle Scholar
  14. 14.
    Palao E, Sdl M, Agarrabeitia AR, Esnal I, Bañuelos J, López-Arbeloa Í, Ortiz MJ (2014) Selective lateral Lithiation of methyl BODIPYs: synthesis, Photophysics, and electrochemistry of new Meso Derivatives. Org Lett 16(17):4364–4367CrossRefGoogle Scholar
  15. 15.
    Palao-Utiel E, Montalvillo-Jiménez L, Esnal I, Prieto-Montero R, Agarrabeitia AR, García-Moreno I, Bañuelos J, Ii L-A, Sdl M, Ortiz MJ (2017) Controlling Vilsmeier-Haack processes in meso -methylBODIPYs: a new way to modulate finely photophysical properties in boron dipyrromethenes. Dyes Pigments 141:286–298CrossRefGoogle Scholar
  16. 16.
    Zhang X-F, Yang X, Xu B (2017) PET-based BisBODIPY photosensitizers for highly efficient excited triplet state and singlet oxygen generation: tuning photosensitizing ability by the dihedral angles. Phys Chem Chem Phys 19(36):24792–24804CrossRefGoogle Scholar
  17. 17.
    Zhang X-F, Yang X (2013) Singlet oxygen generation and triplet excited state spectra of brominated BODIPY. J Phys Chem B 117(18):5533–5539CrossRefGoogle Scholar
  18. 18.
    Zhang X-F, Yang X (2013) Photosensitizer that selectively generates singlet oxygen in nonpolar environments: Photophysical mechanism and efficiency for a covalent BODIPY dimer. J Phys Chem B 117(30):9050–9055CrossRefGoogle Scholar
  19. 19.
    Zhang X-F, Feng N (2017) PET-based halogen-free photosensitizers: covalent meso-aryl as electron donors to effectively induce the formation of excited triplet state and singlet oxygen for BODIPY compounds. Chem Asian J 12:2447–2456CrossRefGoogle Scholar
  20. 20.
    Zhang X-F (2017) BisBODIPY as PCT-based halogen free photosensitizers for highly efficient excited triplet state and singlet oxygen formation: tuning the efficiency by different linking positions. Dyes Pigments 146:491–501CrossRefGoogle Scholar
  21. 21.
    Zhang X-F, Zhu J (2019) BODIPY parent compound: fluorescence, singlet oxygen formation and properties revealed by DFT calculations. J Lumin 205:148–157CrossRefGoogle Scholar
  22. 22.
    Zhang X-F, Zhang Y, Liu L (2014) Fluorescence lifetimes and quantum yields of ten rhodamine derivatives: structural effect on emission mechanism in different solvents. J Lumin 145:448–453CrossRefGoogle Scholar
  23. 23.
    Zhang X-F, Zhang J, Liu L (2014) Fluorescence properties of twenty fluorescein Derivatives: lifetime, quantum yield, absorption and emission spectra. J Fluoresc 24:819–826CrossRefGoogle Scholar
  24. 24.
    Kubheka G, Sanusi K, Mack J, Nyokong T (2018) Optical limiting properties of 3,5-dipyrenylvinyleneBODIPY dyes at 532nm. Spectrochim Acta A 191:357–364CrossRefGoogle Scholar
  25. 25.
    Gómez-Durán CFA, García-Moreno I, Costela A, Martin V, Sastre R, Bañuelos J, Arbeloa FL, Arbeloa IL, Peña-Cabrera E (2010) 8-PropargylaminoBODIPY: unprecedented blue-emitting pyrromethene dye. Synthesis, photophysics and laser properties. Chem Commun 46:5103–5105CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2019

Authors and Affiliations

  1. 1.Institute of Applied PhotochemistryHebei Normal University of Science and TechnologyQinhuangdaoChina
  2. 2.MPC TechnologiesHamiltonCanada
  3. 3.Department of Electrical & Computer EngineeringMcMaster UniversityHamiltonCanada

Personalised recommendations