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β-Diketone derivatives: influence of the chelating group on the photophysical and mechanofluorochromic properties

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Abstract

A diphenyl-boron β-diketonate complex was synthesized. Its photophysical properties were studied in solution and in the solid-state, and compared to those of its parent diketone and the corresponding difluoro-boron complex. TD-DFT calculations show that the molecular orbitals involved in the first Franck–Condon transition are very different for the three compounds studied. The difluoro-boron complex is strongly fluorescent in solution, and remains fluorescent in the solid-state. The free diketone turns to be very weakly fluorescent in solution and displays significant Aggregation Induced Enhanced Emission (AIEE) in the crystalline state, which can be explained by a rigidification of the molecule, while the diphenyl-boron complex is weakly fluorescent in solution as well as in the solid-state. For the free diketone and the difluoro-boron complex a mechanofluorochromic response is observed upon grinding the crystalline powder in a mortar, while for the diphenyl-boron complex no fluorescence emission change is detected under these conditions. Overall, this study shows that the nature of the chelating group has a crucial influence on the photophysical and mechanofluorochromic properties of β-diketonate complexes, leading to a wide variety of behaviors within the closely related structures of such derivatives.

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Acknowledgements

This project has received funding from the European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation programme (grant agreement No 715757 MECHANO-FLUO to C. A.) and from the IDEX Paris-Saclay (Ph. D. fellowship to M. L.).

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Authors and Affiliations

  1. PPSM, ENS Cachan, CNRS, Université Paris-Saclay, 94235, Cachan, France

    Marine Louis, Rémi Métivier & Clémence Allain

  2. ICMMO, Université Paris-Sud, CNRS, Université Paris-Saclay, 91405, Orsay, France

    Régis Guillot

Authors
  1. Marine Louis
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  2. Régis Guillot
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  3. Rémi Métivier
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  4. Clémence Allain
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Correspondence to Rémi Métivier or Clémence Allain.

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Louis, M., Guillot, R., Métivier, R. et al. β-Diketone derivatives: influence of the chelating group on the photophysical and mechanofluorochromic properties. Photochem Photobiol Sci 17, 822–828 (2018). https://doi.org/10.1039/c8pp00070k

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  • DOI: https://doi.org/10.1039/c8pp00070k

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