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Abstract <p>Complexes [{Dy<sub><i>x</i></sub>Ln<sub>(2&#xa0;–&#xa0;<i>x</i>)</sub>(H<sub>2</sub>O)<sub>5</sub>(NO<sub>3</sub>)}<sub>2</sub>CB[6]](NO<sub>3</sub>)<sub>4</sub>·HNO<sub>3</sub>·6H<sub>2</sub>O (<i>x</i> = 1, Ln = Eu; <i>x</i> = 0.8, Gd, Ho) (<b>I</b>–<b>III</b>) are synthesized from a mixture of lanthanide nitrates and cucurbit[6]uril (C<sub>36</sub>H<sub>36</sub>N<sub>24</sub>O<sub>16</sub>, CB[6]) in nitric acid on heating to 100°С. According to the X-ray diffraction (XRD) data, in compounds <b>I</b>–<b>III</b> the lanthanide cation coordinates two oxygen atoms of the CB[6] molecule, H<sub>2</sub>O molecules, and nitrate ions. Compounds <b>I</b>–<b>III</b> are characterized by XRD, IR spectroscopy, ICP-OES spectroscopy, and elemental analysis. The coordinates of chromaticity points are determined from the luminescence spectra, and their values are very close to the white light coordinates. This specific feature is a consequence of the presence of two Dy<sup>3+</sup>-centered emission bands with comparable intensities. One of these bands is the hypersensitive transition <sup>4</sup><i>F</i><sub>9/2</sub> → <sup>6</sup><i>H</i><sub>13/2</sub> caused by a relatively high symmetry of the coordination lanthanide environment close to <i>C</i><sub>4<i>v</i></sub>. In addition, a peculiarity of compounds <b>I</b>–<b>III</b> is a strong dependence of the luminescence spectrum on the excitation wavelength. Models of molecular logical devices with a possibility of switching over luminescent signal of irradiation with different wavelengths are proposed on the basis of this phenomenon.</p>

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Supramolecular Lanthanide Complexes with Cucurbituril: Luminescence and Logical Devices

  • 期刊论文

  • 发表日期：

    2025年8月1日

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  • M. I. Rakhmanova,
  • T. S. Sukhikh,
  • E. A. Kovalenko

摘要

Abstract

Complexes [{DyxLn(2 – x)(H2O)5(NO3)}2CB[6]](NO3)4·HNO3·6H2O (x = 1, Ln = Eu; x = 0.8, Gd, Ho) (I–III) are synthesized from a mixture of lanthanide nitrates and cucurbit[6]uril (C36H36N24O16, CB[6]) in nitric acid on heating to 100°С. According to the X-ray diffraction (XRD) data, in compounds I–III the lanthanide cation coordinates two oxygen atoms of the CB[6] molecule, H2O molecules, and nitrate ions. Compounds I–III are characterized by XRD, IR spectroscopy, ICP-OES spectroscopy, and elemental analysis. The coordinates of chromaticity points are determined from the luminescence spectra, and their values are very close to the white light coordinates. This specific feature is a consequence of the presence of two Dy3+-centered emission bands with comparable intensities. One of these bands is the hypersensitive transition 4F9/2 → 6H13/2 caused by a relatively high symmetry of the coordination lanthanide environment close to C4v. In addition, a peculiarity of compounds I–III is a strong dependence of the luminescence spectrum on the excitation wavelength. Models of molecular logical devices with a possibility of switching over luminescent signal of irradiation with different wavelengths are proposed on the basis of this phenomenon.