Studying the Dielectric Properties of the Curcubituril Cavity on the Basis of the Solvatochromic Effect of Styryl Dye upon the Formation of an Inclusion Complex
- Authors: Stepko A.S.1, Lobova N.A.1,2, Lebedev-Stepanov P.V.1,3
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Affiliations:
- Photochemistry Center, Federal Research Center Crystallography and Photonics, Russian Academy of Sciences
- Moscow Institute of Physics and Technology (State University)
- National Research Nuclear University MEPhI
- Issue: Vol 126, No 4 (2019)
- Pages: 309-315
- Section: Spectroscopy and Physics of Atoms and Molecules
- URL: https://ogarev-online.ru/0030-400X/article/view/165956
- DOI: https://doi.org/10.1134/S0030400X19040210
- ID: 165956
Cite item
Abstract
A new approach to the theoretical evaluation of the local dielectric properties of media that contain an organic dye acting as a nanoprobe is proposed. The method is checked so as to evaluate the dielectric properties of the host molecule in a supramolecular inclusion complex from the experimentally measured shift of the optical absorption spectrum of the guest molecules (dye) after the complex formation. Using the Onsager–Liptay model, the dielectric properties of the cucurbit[7]uril cavity was theoretically estimated by analyzing the experimentally measured shift of the absorption spectrum of 1-(3-ammoniopropyl)-4-[(E)-2-(3,4-dimethoxyphenyl)-ethenyl]-pyridinium dication of the dye after it forms a complex with cucurbit[7]uril in an aqueous solution. To parameterize the Onsager–Liptay equation, the positions of the absorption spectral maxima of the dye under study were experimentally measured in the following solvents with known dielectric and optical properties: methanol, ethanol, 1-propanol, 1-butanol, and water. When calculating molecular structures, dipole moments of the ground and excited states, and polarizability, the TD-DFT quantum chemical method with the CAM-B3LYP functional in the 6-311G(d,p) basis set was used within the Gamess (United States) software package. The obtained theoretical value of the effective dielectric permittivity of the cavity (about 13) is in good agreement with the published value.
About the authors
A. S. Stepko
Photochemistry Center, Federal Research Center Crystallography and Photonics,Russian Academy of Sciences
Author for correspondence.
Email: tousen@bk.ru
Russian Federation, Leninskii pr. 59, Moscow, 119333
N. A. Lobova
Photochemistry Center, Federal Research Center Crystallography and Photonics,Russian Academy of Sciences; Moscow Institute of Physics and Technology (State University)
Email: tousen@bk.ru
Russian Federation, Leninskii pr. 59, Moscow, 119333; Institutskii per. 9, Dolgoprudnyi, Moscow oblast, 141701
P. V. Lebedev-Stepanov
Photochemistry Center, Federal Research Center Crystallography and Photonics,Russian Academy of Sciences; National Research Nuclear University MEPhI
Email: tousen@bk.ru
Russian Federation, Leninskii pr. 59, Moscow, 119333; Kashirskoe sh. 30, Moscow, 115409
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