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New fluorenonocrownophanes containing azobenzene: synthesis, properties and interaction with paraquat

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Abstract

New crownophanes containing 2,7-dioxyfluorenone and 4,4′-azobiphenoxy moieties linked by di-, tri-, tetra-, and pentaethylene glycol residues were synthesized. Just in case of obtaining largest crownophane with pentaethyleneglycol linkers, the dimeric cyclization product was also isolated in low yield. Obtained crownophanes, according to 1H NMR spectral data exist in conformations with closed intramolecular cavity in solution. Photoinduced E–Z isomerization of crownophane containing triethylene glycol linkers were investigated. The azobenzene fragment inclusion into crownophane reduces the photoisomerization rate compared to model 4,4′-dimethoxyazobenzene. In all the obtained crownophanes according to NMR, UV–Vis and X-ray data 4,4′-azobiphenoxy fragment is in E-configuration in solution as well as in the solid state. Crystal packing of all crownophanes has distinct feature—stacking arrangement of fluorenone moieties probably due to electrostatic dipole–dipole interactions. The formation of pseudorotaxane-type host–guest complexes of these crownophanes with paraquat dication was detected by FABMS and 1H NMR spectroscopy. UV–Vis spectra show no significant changes upon complex formation.

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Acknowledgments

This article is dedicated to the memory of our colleagues whose life came to an end: Prof. Oleg V. Shishkin and Dr. Mark M. Botoshansky, who took active part in this research, as well as Prof. Nikolay G. Lukyanenko who was supervisor of this work.

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Authors and Affiliations

  1. Department of Fine Organic Synthesis, A.V. Bogatsky Physico-Chemical Institute, National Academy of Sciences of Ukraine, Lustdorfskaya doroga 86, Odessa, 65080, Ukraine

    Alexander Lyapunov, Tatiana Kirichenko & Catherine Kulygina

  2. Department of X-ray Diffraction Studies and Quantum Chemistry, SSI “Institute for Single Crystals”, National Academy of Sciences of Ukraine, Lenina ave. 60, Kharkiv, 61001, Ukraine

    Roman Zubatyuk

  3. Institute of Applied Physics, Academy of Sciences of Moldova, Academy str. 5, MD2028, Chisinau, Moldova

    Marina Fonari

  4. Institute for Chemistry, V. N. Karazin Kharkiv National University, Svobody sq. 4, Kharkiv, 61022, Ukraine

    Alexander Kyrychenko & Andrey Doroshenko

  5. Department of Inorganic Chemistry, V. N. Karazin Kharkiv National University, Svobody sq. 4, Kharkiv, 61022, Ukraine

    Alexander Kyrychenko

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  1. Alexander Lyapunov
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Correspondence to Tatiana Kirichenko.

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Lyapunov, A., Kirichenko, T., Kulygina, C. et al. New fluorenonocrownophanes containing azobenzene: synthesis, properties and interaction with paraquat. J Incl Phenom Macrocycl Chem 81, 499–508 (2015). https://doi.org/10.1007/s10847-015-0484-0

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  • DOI: https://doi.org/10.1007/s10847-015-0484-0

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