X-RAY SPECTRAL AND QUANTUM CHEMICAL STUDY OF THE ELECTRONIC STRUCTURE OF THIACALIX[4]ARENES ANS THEIR ACYCLIC ANALOGS
N. A. Kryuchkova1,2, S. A. Lavrukhina1, G. A. Kostin1,2, L. N. Mazalov1,2, V. G. Torgov1, A. V. Kalinkin3, A. B. Drapailo4
1A. V. Nikolaev Institute of Inorganic Chemistry, Siberian Division, Russian Academy of Sciences, Novosibirsk
2Novosibirsk State University
3G. K. Boreskov Institute of Catalysis, Siberian Division, Russian Academy of Sciences, Novosibirsk
4Institute of Organic Chemistry, National Academy of Sciences of Ukraine, Ukraine, Kiev
Keywords: thiacalix[4]arenes, X-ray photoelectron spectroscopy, X-ray emission spectroscopy, DFT method
Abstract
An X-ray photoelectron and X-ray emission study of the charge state of thiacalix[4]arenes is performed with a comparison with the data of quantum chemical calculations. Relaxation corrections between the Kohn–Sham orbital energies calculated by the DFT method and experimental parameters of the X-ray emission and photoelectron spectra of the studied compounds are estimated. It is shown that the formation of a cyclic aromatic system in thiacalixarenes results in a decrease in the energy of orbitals involving р–π interactions of the bridging sulfur atoms and aromatic moieties, which determines the features of the X-ray emission spectra of the studied compounds.
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