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The internal heavy-atom effect on 3-phenylselanyl and 3-phenyltellanyl BODIPY derivatives studied by transient absorption spectroscopy

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Abstract

Three monosubstituted 3-phenylselanyl and 3-phenyltellanyl BODIPY derivatives were synthesized and their spectroscopic properties were characterized and compared to those of iodine and chlorine-atoms containing analogues as well as an unsubstituted BODIPY derivative. The fluorescence quantum yields were found to decrease, whereas the intersystem crossing quantum yields (ΦISC), determined by transient spectroscopy, increased in the order of the H → Cl → Se/I → Te substitution. The maximum ΦISC, found for the 3-phenyltellanyl derivative, was 59%. The results are interpreted in terms of the internal heavy-atom effect of the substituents.

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References

  1. A. C. Benniston, G. Copley, Lighting the way ahead with boron dipyrromethene (BODIPY) dyes, Phys. Chem. Chem. Phys., 2009, 11, 4124–4131.

    Article  CAS  PubMed  Google Scholar 

  2. M. Benstead, G. H. Mehl, R. W. Boyle, 4,4′-Difluoro-4-bora-3a,4a-diaza-s-indacenes (BODIPYs) as components of novel light active materials, Tetrahedron, 2011, 67, 3573–3601.

    Article  CAS  Google Scholar 

  3. A. Bessette, G. S. Hanan, Design, synthesis and photophysical studies of dipyrromethene-based materials: insights into their applications in organic photovoltaic devices, Chem. Soc. Rev., 2014, 43, 3342–3405.

    Article  CAS  PubMed  Google Scholar 

  4. N. Boens, V. Leen, W. Dehaen, Fluorescent indicators based on BODIPY, Chem. Soc. Rev., 2012, 41, 1130–1172.

    Article  CAS  PubMed  Google Scholar 

  5. A. Kamkaew, S. H. Lim, H. B. Lee, L. V. Kiew, L. Y. Chung, K. Burgess, BODIPY dyes in photodynamic therapy, Chem. Soc. Rev., 2013, 42, 77–88.

    Article  CAS  PubMed  Google Scholar 

  6. A. Loudet, K. Burgess, BODIPY dyes and their derivatives: Syntheses and spectroscopic properties, Chem. Rev., 2007, 107, 4891–4932.

    Article  CAS  PubMed  Google Scholar 

  7. H. Lu, J. Mack, Y. C. Yang, Z. Shen, Structural modification strategies for the rational design of red/NIR region BODIPYs, Chem. Soc. Rev., 2014, 43, 4778–4823.

    Article  CAS  PubMed  Google Scholar 

  8. G. Ulrich, R. Ziessel, A. Harriman, The chemistry of fluorescent bodipy dyes: Versatility unsurpassed, Angew. Chem., Int. Ed., 2008, 47, 1184–1201.

    Article  CAS  Google Scholar 

  9. J. Z. Zhao, W. H. Wu, J. F. Sun, S. Guo, Triplet photosensitizers: from molecular design to applications, Chem. Soc. Rev., 2013, 42, 5323–5351.

    Article  CAS  PubMed  Google Scholar 

  10. T. Yogo, Y. Urano, Y. Ishitsuka, F. Maniwa, T. Nagano, Highly efficient and photostable photosensitizer based on BODIPY chromophore, J. Am. Chem. Soc., 2005, 127, 12162–12163.

    Article  CAS  PubMed  Google Scholar 

  11. P. Klan and J. Wirz, Photochemistry of organic compounds: From concepts to practice, John Wiley & Sons Ltd., Chichester, 2009.

    Book  Google Scholar 

  12. K. N. Solovyov, E. A. Borisevich, Intramolecular heavy-atom effect in the photophysics of organic molecules, Phys.-Usp., 2005, 48, 231–253.

    Article  CAS  Google Scholar 

  13. M. Galletta, S. Campagna, M. Quesada, G. Ulrich, R. Ziessel, The elusive phosphorescence of pyrromethene-BF2 dyes revealed in new multicomponent species containing Ru(II)-terpyridine subunits, Chem. Commun., 2005, 4222–4224.

    Google Scholar 

  14. A. A. Rachford, R. Ziessel, T. Bura, P. Retailleau, F. N. Castellano, Boron Dipyrromethene (BODIPY) Phosphorescence Revealed in Ir(ppy)(2)(bpy-CC-Bodipy)+, Inorg. Chem., 2010, 49, 3730–3736.

    Article  CAS  PubMed  Google Scholar 

  15. S. H. Lim, C. Thivierge, P. Nowak-Sliwinska, J. Y. Han, H. van den Bergh, G. Wagnieres, K. Burgess, H. B. Lee, In vitro and in vivo photocytotoxicity of boron dipyrromethene derivatives for photodynamic therapy, J. Med. Chem., 2010, 53, 2865–2874.

    Article  CAS  PubMed  Google Scholar 

  16. W. H. Wu, H. M. Guo, W. T. Wu, S. M. Ji, J. Z. Zhao, Organic triplet sensitizer library derived from a single chromophore (BODIPY) with long-lived triplet excited state for triplet-triplet annihilation based upconversion, J. Org. Chem., 2011, 76, 7056–7064.

    Article  CAS  PubMed  Google Scholar 

  17. Y. Cakmak, S. Kolemen, S. Duman, Y. Dede, Y. Dolen, B. Kilic, Z. Kostereli, L. T. Yildirim, A. L. Dogan, D. Guc, E. U. Akkaya, Designing excited states: Theory-guided access to efficient photosensitizers for photodynamic action, Angew. Chem., Int. Ed., 2011, 50, 11937–11941.

    Article  CAS  Google Scholar 

  18. S. Duman, Y. Cakmak, S. Kolemen, E. U. Akkaya, Y. Dede, Heavy atom free singlet oxygen generation: Doubly substituted configurations dominate S1 states of bis-BODIPYs, J. Org. Chem., 2012, 77, 4516–4527.

    Article  CAS  PubMed  Google Scholar 

  19. M. Broring, R. Kruger, S. Link, C. Kleeberg, S. Kohler, X. Xie, B. Ventura, L. Flamigni, Bis(BF(2))-2,2 ‘-bidipyrrins (BisBODIPYs): Highly fluorescent BODIPY dimers with large Stokes shifts, Chem. - Eur. J., 2008, 14, 2976–2983.

    Article  PubMed  CAS  Google Scholar 

  20. B. Ventura, G. Marconi, M. Broring, R. Krugerb, L. Flamigni, Bis(BF2)-2,2 ‘-bidipyrrins, a class of BODIPY dyes with new spectroscopic and photophysical properties, New J. Chem., 2009, 33, 428–438.

    Article  CAS  Google Scholar 

  21. K. Koenig, Multiphoton microscopy in life sciences, J. Microsc., 2000, 200, 83–104.

    Article  Google Scholar 

  22. A. J. Mukherjee, S. S. Zade, H. B. Singh, R. B. Sunoj, Organoselenium chemistry: Role of intramolecular interactions, Chem. Rev., 2010, 110, 4357–4416.

    Article  CAS  PubMed  Google Scholar 

  23. S. T. Manjare, Y. Kim, D. G. Churchill, Selenium- and tellurium-containing fluorescent molecular probes for the detection of biologically important analytes, Acc. Chem. Res., 2014, 47, 2985–2998.

    Article  CAS  PubMed  Google Scholar 

  24. C. W. Nogueira, G. Zeni, J. B. T. Rocha, Organoselenium and organotellurium compounds: Toxicology and pharmacology, Chem. Rev., 2004, 104, 6255–6285.

    Article  CAS  PubMed  Google Scholar 

  25. B. Tang, Y. L. Xing, P. Li, N. Zhang, F. B. Yu, G. W. Yang, A rhodamine-based fluorescent probe containing a Se-N bond for detecting thiols and its application in living cells, J. Am. Chem. Soc., 2007, 129, 11666–11667.

    Article  CAS  PubMed  Google Scholar 

  26. Z. R. Lou, P. Li, X. F. Sun, S. Q. Yang, B. S. Wang, K. L. Han, A fluorescent probe for rapid detection of thiols and imaging of thiols reducing repair and H2O2 oxidative stress cycles in living cells, Chem. Commun., 2013, 49, 391–393.

    Article  CAS  Google Scholar 

  27. S. J. Balkrishna, A. S. Hodage, S. Kumar, P. Panini, Sensitive and regenerable organochalcogen probes for the colorimetric detection of thiols, RSC Adv., 2014, 4, 11535–11538.

    Article  CAS  Google Scholar 

  28. B. S. Wang, P. Li, F. B. Yu, J. S. Chen, Z. J. Qu, K. L. Han, A near-infrared reversible and ratiometric fluorescent probe based on Se-BODIPY for the redox cycle mediated by hypobromous acid and hydrogen sulfide in living cells, Chem. Commun., 2013, 49, 5790–5792.

    Article  CAS  Google Scholar 

  29. S. T. Manjare, S. Kim, W. Do Heo, D. G. Churchill, Selective and sensitive superoxide detection with a new diselenide-based molecular probe in living breast cancer cells, Org. Lett., 2014, 16, 410–412.

    Article  CAS  PubMed  Google Scholar 

  30. E. Fron, E. Coutino-Gonzalez, L. Pandey, M. Sliwa, M. Van der Auweraer, F. C. De Schryver, J. Thomas, Z. Y. Dong, V. Leen, M. Smet, W. Dehaen, T. Vosch, Synthesis and photophysical characterization of chalcogen substituted BODIPY dyes, New J. Chem., 2009, 33, 1490–1496.

    Article  CAS  Google Scholar 

  31. S. T. Manjare, J. Kim, Y. Lee, D. G. Churchill, Facile meso-BODIPY annulation and selective sensing of hypochlorite in water, Org. Lett., 2014, 16, 520–523.

    Article  CAS  PubMed  Google Scholar 

  32. V. Leen, E. Braeken, K. Luckermans, C. Jackers, M. Van der Auweraer, N. Boens, W. Dehaen, A versatile, modular synthesis of monofunctionalized BODIPY dyes, Chem. Commun., 2009, 4515–4517.

    Google Scholar 

  33. V. Leen, T. Leemans, N. Boens, W. Dehaen, 2- and 3-Monohalogenated BODIPY dyes and their functionalized analogues: Synthesis and spectroscopy, Eur. J. Org. Chem., 2011, 4386–4396.

    Google Scholar 

  34. M. Kollmannsberger, T. Gareis, S. Heinl, J. Breu, J. Daub, Electrogenerated chemiluminescence and proton-dependent switching of fluorescence: Functionalized difluoroboradiaza-s-indacenes, Angew. Chem., Int. Ed. Engl., 1997, 36, 1333–1335.

    Article  CAS  Google Scholar 

  35. X. F. Zhang, X. D. Yang, Singlet oxygen generation and triplet excited-state spectra of brominated BODIPY, J. Phys. Chem. B, 2013, 117, 5533–5539.

    Article  CAS  PubMed  Google Scholar 

  36. R. Bonneau, I. Carmichael, G. L. Hug, Molar absorption coefficients of transient species in solution, Pure Appl. Chem., 1991, 63, 290–299.

    Article  Google Scholar 

  37. C. Tahtaoui, C. Thomas, F. Rohmer, P. Klotz, G. Duportail, Y. Mely, D. Bonnet, M. Hibert, Convenient method to access new 4,4-dialkoxy- and 4,4-diaryloxy-diaza-s-indacene dyes: Synthesis and spectroscopic evaluation, J. Org. Chem., 2007, 72, 269–272.

    Article  CAS  PubMed  Google Scholar 

  38. Y. H. Chen, J. Z. Zhao, L. J. Xie, H. M. Guo, Q. T. Li, Thienyl-substituted BODIPYs with strong visible light-absorption and long-lived triplet excited states as organic triplet sensitizers for triplet-triplet annihilation upconversion, RSC Adv., 2012, 2, 3942–3953.

    Article  CAS  Google Scholar 

  39. H. L. Kee, C. Kirmaier, L. H. Yu, P. Thamyongkit, W. J. Youngblood, M. E. Calder, L. Ramos, B. C. Noll, D. F. Bocian, W. R. Scheidt, R. R. Birge, J. S. Lindsey, D. Holten, Structural control of the photodynamics of boron-dipyrrin complexes, J. Phys. Chem. B, 2005, 109, 20433–20443.

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  40. M. J. Ortiz, A. R. Agarrabeitia, G. Duran-Sampedro, J. B. Prieto, T. A. Lopez, W. A. Massad, H. A. Montejano, N. A. Garcia, I. L. Arbeloa, Synthesis and functionalization of new polyhalogenated BODIPY dyes. Study of their photophysical properties and singlet oxygen generation, Tetrahedron, 2012, 68, 1153–1162.

    Article  CAS  Google Scholar 

  41. V. Lakshmi, M. R. Rao, M. Ravikanth, Halogenated boron-dipyrromethenes: synthesis, properties and applications, Org. Biomol. Chem., 2015, 13, 2501–2517.

    Article  CAS  PubMed  Google Scholar 

  42. T. Rohand, W. W. Qin, N. Boens, W. Dehaen, Palladium-catalyzed coupling reactions for the functionalization of BODIPY dyes with fluorescence spanning the visible spectrum, Eur. J. Org. Chem., 2006, 4658–4663.

    Google Scholar 

  43. M. Zander, The intra-annular internal heavy-atom effect on the fluorescence and phosphorescence properties of oxygen, sulphur or selenium containing heterocyclic systems related to dibenzo[b,n]perylene, Z. Naturforsch., A: Phys. Sci., 1989, 44, 1116–1118.

    Article  CAS  Google Scholar 

  44. M. Zander, G. Kirsch, On the phosphorescence of benzologues of furan, thiophene, selenophene, and tellurophene. A systematic study of the intra-annular internal heavy-atom effect, Z. Naturforsch., A: Phys. Sci., 1989, 44, 205–209.

    Article  CAS  Google Scholar 

  45. Z. Shen, H. Rohr, K. Rurack, H. Uno, M. Spieles, B. Schulz, G. Reck, N. Ono, Boron-diindomethene (BDI) dyes and their tetrahydrobicyclo precursors - en route to a new class of highly emissive fluorophores for the red spectral range, Chem. - Eur. J., 2004, 10, 4853–4871.

    Article  CAS  PubMed  Google Scholar 

  46. S. Hattori, K. Ohkubo, Y. Urano, H. Sunahara, T. Nagano, Y. Wada, N. V. Tkachenko, H. Lemmetyinen, S. Fukuzumi, Charge separation in a nonfluorescent donor-acceptor dyad derived from boron dipyrromethene dye, leading to photocurrent generation, J. Phys. Chem. B, 2005, 109, 15368–15375.

    Article  CAS  PubMed  Google Scholar 

  47. L. Klicova, P. Sebej, T. Solomek, B. Hellrung, P. Slavicek, P. Klan, D. Heger, J. Wirz, Adiabatic triplet state tautomerization of p-hydroxyacetophenone in aqueous solution, J. Phys. Chem. A, 2012, 116, 2935–2944.

    Article  CAS  PubMed  Google Scholar 

  48. C. V. Kumar, L. Qin, P. K. Das, Aromatic thioketone triplets and their quenching behaviour towards oxygen and di-t-butylnitroxy radical. A laser-flash-photolysis study, J. Chem. Soc., Faraday Trans. 2, 1984, 80, 783–793.

    Article  CAS  Google Scholar 

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Correspondence to Petr Klán.

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Electronic supplementary information (ESI) available. See DOI: 10.1039/c5pp00366k

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Al Anshori, J., Slanina, T., Palao, E. et al. The internal heavy-atom effect on 3-phenylselanyl and 3-phenyltellanyl BODIPY derivatives studied by transient absorption spectroscopy. Photochem Photobiol Sci 15, 250–259 (2016). https://doi.org/10.1039/c5pp00366k

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