Abstract
The IR spectra of p-(3-carboxy-1-adamantyl)-calix[4]arene (AdC4A) were studied. Using IR spectroscopy, it has been shown that in calixarene in dilute solution in CCl4, there was no free hydroxyl absorption band. The hydroxyl group band was characterized by a very low frequency, which indicates a strong intramolecular hydrogen bond on the lower rim of the calixarene molecules. On the upper rim of the calixarene, the carboxyl groups form cyclic dimer or tetramer complexes via intermolecular hydrogen bonds. The cone conformation persists, but there is a mutual influence of the hydrogen bonds along the top and bottom rims of the calixarene molecule. The structure with dimeric hydrogen bonds between the carboxyl groups is 16.5 KJ/mol more preferable than the structure with tetrameric cyclic hydrogen bonds for AdC4A. The reactivity depends on the type of association on the upper rim, whether these are hydrogen-bonded dimers or cyclic tetrameric association.
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Acknowledgments
The authors are grateful to the Assigned Spectral-Analytical Center of FRC Kazan Scientific Center of RAS for technical assistance in research.
Funding
Contributions to research were funded by the state assignment to: Federal Scientific Center “Scientific Research Institute for System Analysis of the RAS” (CDV) and A.E. Arbuzov Institute of Organic and Physical Chemistry RAS (V.I.K.).
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Furer, V.L., Potapova, L.I., Chachkov, D.V. et al. Study of p-(3-carboxy-1-adamantyl)-calix[4]arene with hydrogen bonds along the upper and lower rim by IR spectroscopy and DFT. J Mol Model 26, 179 (2020). https://doi.org/10.1007/s00894-020-04441-1
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DOI: https://doi.org/10.1007/s00894-020-04441-1