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Halogen…π interactions in the complexes of fluorenonophane with haloforms

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Abstract

The study of two complexes of fluorenonophane with CHCl3 and CHBr3 molecules has revealed that they differ mainly by the halogen bonds between host and guest molecules. The experimental and theoretical quantum chemical study has shown that the strength of a halogen bond depends on the nature of a halogen atom as well as its orientation to the π-system. The more positive electrostatic potential was revealed at the bromine atom indicating the stronger halogen bond with its participation that was confirmed by the interaction energies calculated for corresponding dimers and the evaluation of the true energy of a halogen bond. The orientation of the chlorine atom at the carbon aromatic atom instead of the center of the benzene ring leads to the shortest Hal…C distance that points out the stronger interaction according to the geometrical characteristics. The EDA analysis of the fluorenonophane complexes with CHCl3 and CHBr3 and their analogs with one halogen atom replaced by the hydrogen atom allows us to presume that the nature of halogen bonding is rather dispersive than electrostatic.

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Availability of data and materials

Experimental X-ray diffraction data are available from the Cambridge Crystallographic Data Centre on request quoting the deposition numbers CCDC 647,971 for 3Cl and CCDC 2,098,245 for 3Br.

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Funding

The authors were financially supported by the National Academy of Sciences of Ukraine in the frame of the projects “New supramolecular systems based on cyclophanes with fluorenone and benzimidazole fragments. Design, synthesis, structure, perspectives” (0120U100122) and “Functional materials for biomedical purposes based on halogen-containing organic compounds” (0120U102660).

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Authors and Affiliations

  1. SSI “Institute for Single Crystals” National Academy of Sciences of Ukraine, 60 Nauky ave, Kharkiv, 61001, Ukraine

    Svitlana V. Shishkina, Viktoriya V. Dyakonenko, Oleg V. Shishkin & Volodimir P. Semynozhenko

  2. V. N. Karazin, Svobody Sq, Kharkiv National University, Kharkiv, 61112, Ukraine

    Svitlana V. Shishkina & Oleg V. Shishkin

  3. A. V. Bogatsky Physico-Chemical Institute, National Academy of Sciences of Ukraine, 86 Lustdorfskaya doroga, Odesa, Ukraine

    Tatiana Yu. Bogashchenko, Alexander Yu. Lyapunov & Tatiana I. Kirichenko

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  1. Svitlana V. Shishkina
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  2. Viktoriya V. Dyakonenko
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  3. Oleg V. Shishkin
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  4. Volodimir P. Semynozhenko
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  5. Tatiana Yu. Bogashchenko
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  6. Alexander Yu. Lyapunov
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Contributions

S. Shishkina analyzed the results and wrote the manuscript, V. Dyakonenko performed the study of electron density distribution and decomposition of the interaction energy analysis, O. Shishkin performed the X-ray diffraction study and wrote the analysis of molecular structure, V. Seminozhenko discussed the idea and its realization, T. Bogashchenko synthesized the studied compounds, A. Lyapunov performed the spectral study of complexes, and T. Kirichenko discussed the results and wrote the manuscript.

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Correspondence to Svitlana V. Shishkina.

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Shishkina, S.V., Dyakonenko, V.V., Shishkin, O.V. et al. Halogen…π interactions in the complexes of fluorenonophane with haloforms. Struct Chem 33, 257–266 (2022). https://doi.org/10.1007/s11224-021-01839-2

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