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IR and NMR spectra, intramolecular hydrogen bonding and conformations of mercaptothiacalix[4]arene molecules and their para-tert-butyl-derivative

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Abstract

It is demonstrated that the introduction of p-tert-butyl groups dramatically influences the conformational behaviour of the mercaptothiacalix[4]arene molecules. Quantum-chemical computations in combination with IR and NMR spectroscopy prove that, in contrast to closely related calixarenes, the 1,3-alternate becomes a dominant conformer of p-tert-butyl-mercaptothiacalix[4]arene not only in crystal, but also in solutions and in vacuum. It is shown that the title molecules form essentially non-cooperative intramolecular hydrogen bonds: their SH groups are intramolecularly H-bonded solely to the sulfide groups bridging thiophenolic units. The enthalpy of this bonding, evaluated from Iogansen’s rule, amounts to ca. 1.5 kcal mol−1 per one SH···S bond, which about four times smaller than the enthalpies of cooperative intramolecular H-bonds formed by related calixarenes and thiacalixarenes.

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Acknowledgements

The authors are indebted to all staff-members of the Supercomputer centre of the Kazan Scientific Centre of the Russian Academy of Sciences and especially to Dr. D. Chachkov for technical assistance in the computations and valuable advice. Special thanks are due to Dr. M.A. Tafipolsky for permission to use his version of the program, adopted from Sipachev [17].

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Authors and Affiliations

  1. A.E.Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Centre of the Russian Academy of Sciences, Arbuzov str. 8, Kazan, 420088, Russia

    Sergey A. Katsyuba, Elena E. Zvereva, Alla V. Chernova, Artur R. Shagidullin, Svetlana E. Solovieva, Igor S. Antipin & Alexander I. Konovalov

  2. Kazan State University, Kremlevskaja str. 18, Kazan, 420008, Russia

    Artur R. Shagidullin, Igor S. Antipin & Alexander I. Konovalov

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  1. Sergey A. Katsyuba
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  2. Elena E. Zvereva
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  3. Alla V. Chernova
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Correspondence to Sergey A. Katsyuba.

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Katsyuba, S.A., Zvereva, E.E., Chernova, A.V. et al. IR and NMR spectra, intramolecular hydrogen bonding and conformations of mercaptothiacalix[4]arene molecules and their para-tert-butyl-derivative. J Incl Phenom Macrocycl Chem 60, 281–291 (2008). https://doi.org/10.1007/s10847-007-9376-2

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