Skip to main content
SpringerLink
Log in

Blue fluorescence from N,O-coordinated BF2 complexes having aromatic chromophores in solution and the solid state

  • Paper
  • Published:
Photochemical & Photobiological Sciences Aims and scope Submit manuscript

Abstract

We prepared amide-heterocycle (HC) compounds having various aromatic π-electron systems (Ar), such as phenyl, naphthyl, furyl, thienyl and phenanthryl moieties, and converted them as ligands to difluoroboronated complexes, Ar@HCs. Blue fluorescence from Ar@HCs was observed in solution and the solid state, and the fluorescence quantum yields (Φf) and lifetimes (τf) were determined. The Φf values in CHCl3 were as small as 0.1 except for the phenanthrene derivatives (0.4–0.6). Observation of the triplet–triplet absorption upon laser flash photolysis of Ar@HCs in solution indicated that the fluorescence process competes with intersystem crossing to the triplet state. Blue fluorescence in the solid state was observed with the Φf values of 0.3–0.7. Based on the crystallographic data, the relationship between the crystal structures and emission features of Ar@HCs in the solid state is discussed.

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

Similar content being viewed by others

References

  1. R. P. Haugland, Handbook of fluorescent probes and research chemicals, Molecular Probe Inc., Eugene, OR, 9th edn, 2002.

    Google Scholar 

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

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  4. D. Frath, J. Massue, G. Ulrich and R. Ziessel, Luminescent materials: Locking π-conjugated and heterocyclic ligands with boron(III), Angew. Chem., Int. Ed., 2014, 53, 2290–2310.

    Article  CAS  Google Scholar 

  5. C. S. Kue, S. Y. Ng, S. H. Voon, A. Kamkaew, L. Y. Chung, L. V. Kiew and H. B. Lee, Recent strategies to improve boron dipyrromethene (BODIPY) for photodynamic cancer therapy: An updated review, Photochem. Photobiol. Sci., 2018, 17, 1691–1708.

    Article  CAS  Google Scholar 

  6. K. Ono, K. Yoshikawa, Y. Tsuji, H. Yamaguchi, R. Uozumi, M. Tomura, K. Taga and K. Saito, Synthesis and photo- luminescence properties of bf2 complexes with 1,3-diketone ligands, Tetrahedron, 2007, 63, 9354–9358.

    Article  CAS  Google Scholar 

  7. A. G. Mirochnik, E. V. Gukhman, V. E. Karasev and P. A. Zhikhareva, Fluorescence and photochemical properties of crystalline boron difluorides β-diketonato, Russ. Chem. Bull., 2000, 49, 1024–1027.

    Article  CAS  Google Scholar 

  8. A. Sakai, M. Tanaka, E. Ohta, Y. Yoshimoto, K. Mizuno and H. Ikeda, White light emission from a single component system: Remarkable concentration effects on the fluorescence of 1,3-diaroylmethanatoboron difluoride, Tetrahedron Lett., 2012, 53, 4138–4141.

    Article  CAS  Google Scholar 

  9. E. Cogné-Laage, J.-F. Allemand, O. Ruel, J.-B. Baudin, V. Croquette, M. Blanchard-Desce and L. Jullien, Diaroyl (methanato)boron difluoride compounds as medium-sensitive two-photon fluorescent probes, Chem. – Eur. J., 2004, 10, 1445–1455.

    Article  Google Scholar 

  10. T. Liu, A. D. Chien, J. Lu, G. Zhang and C. L. Fraser, Arene effects on difluoroboron β-diketonate mechanochromic luminescence, J. Mater. Chem., 2011, 21, 8401–8408.

    Article  CAS  Google Scholar 

  11. S. Xu, R. E. Evans, T. Liu, G. Zhang, J. N. Demas, C. O. Trindle and C. L. Fraser, Aromatic difluoroboron β-diketonate complexes: Effects of π-conjugation and media on optical properties, Inorg. Chem., 2013, 52, 3597–3610.

    Article  CAS  Google Scholar 

  12. M. Mamiya, Y. Suwa, H. Okamoto and M. Yamaji, Preparation and photophysical properties of fluorescent difluoroboronated β-diketones having phenanthrene moieties studied by emission and transient absorption measurements, Photochem. Photobiol. Sci., 2016, 15, 278–286.

    Article  CAS  Google Scholar 

  13. H.-W. Mo, Y. Tsuchiya, Y. Geng, T. Sagawa, C. Kikuchi, H. Nakanotani, F. Ito and C. Adachi, Color tuning of avobenzone boron difluoride as an emitter to achieve fullcolor emission, Adv. Funct. Mater., 2016, 26, 6703–6710.

    Article  CAS  Google Scholar 

  14. H. Sasabe, K. Sasaki, M. Mamiya, Y. Suwa, T. Watanabe, N. Onuma, K. Nakao, M. Yamaji and J. Kido, Unique solidstate emission behaviors of aromatic difluoroboronated β-diketones as an emitter in organic light-emitting devices, Chem. – Asian J., 2017, 12, 2299–2303.

    CAS  Google Scholar 

  15. M. Yamaji, S.-i. Kato, K. Tomonari, M. Mamiya, K. Goto, H. Okamoto, Y. Nakamura and F. Tani, Blue fluorescence from BF2 complexes of N,O-benzamide ligands: Synthesis, structure, and photophysical properties, Inorg. Chem., 2017, 56, 12514–12519.

    CAS  Google Scholar 

  16. M. Yamaji, Y. Aihara, T. Itoh, S. Tobita and H. Shizuka, Thermochemical profiles on hydrogen atom transfer from triplet naphthol and proton-induced electron transfer from triplet methoxynaphthalene to benzophenone via triplet exciplexes studied by laser flash photolysis, J. Phys. Chem., 1994, 98, 7014–7021.

    Article  CAS  Google Scholar 

  17. M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G. A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H. P. Hratchian, A. F. Izmaylov, J. Bloino, G. Zheng, J. L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, J. J. A. Montgomery, J. E. Peralta, F. Ogliaro, M. Bearpark, J. J. Heyd, E. Brothers, K. N. Kudin, V. N. Staroverov, T. Keith, R. Kobayashi, J. Normand, K. Raghavachari, A. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, N. Rega, J. M. Millam, M. Klene, J. E. Knox, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, R. L. Martin, K. Morokuma, V. G. Zakrzewski, G. A. Voth, P. Salvador, J. J. Dannenberg, S. Dapprich, A. D. Daniels, O. Farkas, J. B. Foresman, J. V. Ortiz, J. Cioslowski and D. J. Fox, Gaussian 09, Revision D.01, Gaussian, Inc., Wallingford CT, 2010.

    Google Scholar 

  18. M. Mamiya, Y. Suwa, H. Okamoto and M. Yamaji, Photochemically-assisted synthesis and photophysical properties of difluoroboronated β-diketones with fused fourbenzenering chromophores, chrysene and pyrene, Photochem. Photobiol. Sci., 2016, 15, 928–936.

    Article  CAS  Google Scholar 

  19. S. J. Strickler and R. A. Berg, Relationship between absorption intensity and fluorescence lifetime of molecules, J. Phys. Chem., 1962, 37, 814–822.

    Article  CAS  Google Scholar 

  20. A. Sakai, E. Ohta, Y. Yoshimoto, M. Tanaka, Y. Matsui, K. Mizuno and H. Ikeda, New fluorescence domain “excited multimer” formed upon photoexcitation of continuously stacked diaroylmethanatoboron difluoride molecules with fused π-orbitals in crystals, Chem. – Eur. J., 2015, 21, 18128–18137.

    Article  CAS  Google Scholar 

  21. S. Hachiya, D. Hashizume, H. Ikeda, M. Yamaji, S. Maki, H. Niwa and T. Hirano, Spectroscopic properties of BF2 complexes of N,-(5-phenyl-2-pyrazinyl)pivalamides exhibiting fluorescence in solution and solid state, J. Photochem. Photobiol., A, 2016, 331, 206–214.

    CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Division of Molecular Science, Graduate School of Science and Technology, Gunma University, 373-0057, Ota, Gunma, Japan

    Minoru Yamaji

  2. Education Program of Materials and Bioscience, Graduate School of Science and Technology, Gunma University, 376-8515, Kiryu, Gunma, Japan

    Kazuhiro Tomonari & Keisuke Ikuma

  3. Institute for Materials Chemistry and Engineering, Kyushu University, 819-0395, Fukuoka, Japan

    Kenta Goto & Fumito Tani

  4. Division of Earth, Life, and Molecular Sciences, Graduate School of Natural Sciences and Technology, Okayama University, 700-8530, Okayama, Japan

    Hideki Okamoto

Authors
  1. Minoru Yamaji
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Kazuhiro Tomonari
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Keisuke Ikuma
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Kenta Goto
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Fumito Tani
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Hideki Okamoto
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Minoru Yamaji.

Additional information

Electronic supplementary information (ESI) available: The precise synthesis procedures and NMR and HRMS data, the decay profiles of fluorescence, results of DFT calculations including tables of atom coordinates for the optimized geometries, X-ray crystallographic analysis data, and 1H and 13C NMR spectra of the compounds prepared in the present work. CCDC 1881146–1881152 and 1880203. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c9pp00410f

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Yamaji, M., Tomonari, K., Ikuma, K. et al. Blue fluorescence from N,O-coordinated BF2 complexes having aromatic chromophores in solution and the solid state. Photochem Photobiol Sci 18, 2884–2892 (2019). https://doi.org/10.1039/c9pp00410f

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1039/c9pp00410f

Search

Navigation