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Journal of Structural Chemistry

, Volume 58, Issue 5, pp 866–875 | Cite as

Electronic structure of functionalized thia- and calix[4]arenes

  • L. N. MazalovEmail author
  • S. A. Lavrukhina
  • A. D. Fedorenko
  • G. I. Semushkina
  • A. V. Kalinkin
Article
  • 61 Downloads

Abstract

The electronic structure of calix[4]arene phosphine oxides (CPO) and thiacalix[4]arene phosphine oxides (TCPO) is studied by X-ray photoelectron and emission spectroscopy and quantum chemical methods. The electron density distribution over atoms contained in CPO and TCPO is analyzed. The structure of higher occupied molecular orbitals (HOMO) is examined. It is shown that HOMOs of these compounds mainly consist of contributions of oxygen 2p atomic orbitals (AOs) of phosphoryl and hydroxyl moieties and also bridging sulfur 3p AOs, which indicates the bifunctionality of the considered extractant molecules. The mutual effect of the lower and upper rims of CPOs and TCPOs as well as the effect of their structures on the electron density distribution over calixarene molecules is investigated.

Keywords

X-ray emission spectroscopy X-ray photoelectron spectroscopy quantum chemical calculations DFT method calix[4]arene phosphine oxides thiacalix[4]arene phosphine oxides extractant 

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Copyright information

© Pleiades Publishing, Ltd. 2017

Authors and Affiliations

  • L. N. Mazalov
    • 1
    • 3
    Email author
  • S. A. Lavrukhina
    • 1
  • A. D. Fedorenko
    • 1
  • G. I. Semushkina
    • 1
  • A. V. Kalinkin
    • 2
  1. 1.Nikolaev Institute of Inorganic Chemistry, Siberian BranchRussian Academy of SciencesNovosibirskRussia
  2. 2.Boreskov Institute of Catalysis, Siberian BranchRussian Academy of SciencesNovosibirskRussia
  3. 3.Novosibirsk National Research State UniversityNovosibirskRussia

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