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Study of the self-association of molecular tweezers bearing two different arms: influence of the stereoelectronic effects of the arm substituents

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Abstract

In the general field of molecular recognition, the self-assembly of a tweezer bearing a R(+) usnic acid arm and a substituted 1,8-naphthalimide moiety as a second arm was investigated through a 1H NMR study. Two self-association modes were evidenced: either the usnic acid arms (mode A) or the naphthalimide ones (mode B) were face to face in the center of the dimer. The existence of a third non-symmetrical mode (mode C) has not been evidenced experimentally. The behavior of these tweezers was discussed taking into account the electronic density of the naphtalimide arms and the slow mode A/mode B exchange rate (EXSY experiments). Only the mode A was observed when naphthalimide was either non-substituted (1) or substituted by Br (2). With one or two electrodonating substituents (OCH3 (3) or (OCH3)2 (4) or N(CH3)2 (5)) both modes A and B occured in a 50/50 ratio. This ratio depended on temperature for tweezer 3.

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Acknowledgements

The authors Pr D. Jacquemin and Dr J. Graton (CEISAM, Nantes, France) for fruitful discussions, Dr P. Jéhan (SCANMAT, Rennes, France) for mass spectrometry and Dr N. Levoin (Bioprojet-Biotech, France) for charge calculations. We are most grateful to the PRISM core facility (Rennes-Angers, France) for NMR spectrometer access.

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Authors and Affiliations

  1. Univ Rennes, CNRS, ISCR– UMR 6226, 35043, Rennes, France

    Béatrice Legouin, Arnaud Bondon, Solenn Ferron & Philippe Uriac

  2. SCANMAT, 35042, Rennes, France

    Clément Orione

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  1. Béatrice Legouin
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  2. Arnaud Bondon
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Correspondence to Béatrice Legouin.

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Legouin, B., Bondon, A., Orione, C. et al. Study of the self-association of molecular tweezers bearing two different arms: influence of the stereoelectronic effects of the arm substituents. J Incl Phenom Macrocycl Chem 96, 101–109 (2020). https://doi.org/10.1007/s10847-019-00954-2

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