Modulating the Inclusive and Coordinating Ability of Thiacalix[4]arene and Its Antenna Effect on Yb<sup>3</sup>-Luminescence via Upper-Rim Substitution<xref rid="fn+-20221012160304-1908848" ref-type="fn">+</xref>
The present work introduces the series of thiacalix[4]arenes (H<sub>4</sub>L) bearing different upper-rim substituents (R = H, Br, NO<sub>2</sub>) for rational design of ligands providing an antenna-effect on the NIR Yb<sup>3+</sup>-centered luminescence of their...
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| Format: | Article |
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MDPI AG
2022-10-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/27/20/6793 |
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| author | Sergey N. Podyachev Svetlana N. Sudakova Rustem R. Zairov Victor V. Syakaev Alexey N. Masliy Michal Dusek Aidar T. Gubaidullin Alexey P. Dovzhenko Daina N. Buzyurova Dmitry V. Lapaev Gulnaz Sh. Mambetova Vasily M. Babaev Andrey M. Kuznetsov Asiya R. Mustafina |
| author_facet | Sergey N. Podyachev Svetlana N. Sudakova Rustem R. Zairov Victor V. Syakaev Alexey N. Masliy Michal Dusek Aidar T. Gubaidullin Alexey P. Dovzhenko Daina N. Buzyurova Dmitry V. Lapaev Gulnaz Sh. Mambetova Vasily M. Babaev Andrey M. Kuznetsov Asiya R. Mustafina |
| author_sort | Sergey N. Podyachev |
| collection | DOAJ |
| description | The present work introduces the series of thiacalix[4]arenes (H<sub>4</sub>L) bearing different upper-rim substituents (R = H, Br, NO<sub>2</sub>) for rational design of ligands providing an antenna-effect on the NIR Yb<sup>3+</sup>-centered luminescence of their Yb<sup>3+</sup> complexes. The unusual inclusive self-assembly of H<sub>3</sub>L<sup>−</sup> (Br) through Br<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mi mathvariant="sans-serif">π</mi></semantics></math></inline-formula> interactions is revealed through single-crystal XRD analysis. Thermodynamically favorable formation of dimeric complexes [2Yb<sup>3+</sup>:2HL<sup>3−</sup>] leads to efficient sensitizing of the Yb<sup>3+</sup> luminescence for H<sub>4</sub>L (Br, NO<sub>2</sub>), while poor sensitizing is observed for ligand H<sub>4</sub>L (H). X-ray analysis of the single crystal separated from the basified DMF solutions of YbCl<sub>3</sub> and H<sub>4</sub>L(NO<sub>2</sub>) has revealed the transformation of the dimeric complexes into [4Yb<sup>3+</sup>:2L<sup>4−</sup>] ones with a cubane-like cluster structure. The luminescence characteristics of the complexes in the solutions reveal the peculiar antenna effect of H<sub>4</sub>L(R = NO<sub>2</sub>), where the triplet level at 567 nm (17,637 cm<sup>−1</sup>) arisen from ILCT provides efficient sensitizing of the Yb<sup>3+</sup> luminescence. |
| first_indexed | 2024-03-09T19:43:49Z |
| format | Article |
| id | doaj.art-de760bb87a4f45c9a50fe3e613feff68 |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-09T19:43:49Z |
| publishDate | 2022-10-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-de760bb87a4f45c9a50fe3e613feff682023-11-24T01:31:09ZengMDPI AGMolecules1420-30492022-10-012720679310.3390/molecules27206793Modulating the Inclusive and Coordinating Ability of Thiacalix[4]arene and Its Antenna Effect on Yb<sup>3</sup>-Luminescence via Upper-Rim Substitution<xref rid="fn+-20221012160304-1908848" ref-type="fn">+</xref>Sergey N. Podyachev0Svetlana N. Sudakova1Rustem R. Zairov2Victor V. Syakaev3Alexey N. Masliy4Michal Dusek5Aidar T. Gubaidullin6Alexey P. Dovzhenko7Daina N. Buzyurova8Dmitry V. Lapaev9Gulnaz Sh. Mambetova10Vasily M. Babaev11Andrey M. Kuznetsov12Asiya R. Mustafina13Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center of RAS, Arbuzov Str. 8, 420088 Kazan, Russia Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center of RAS, Arbuzov Str. 8, 420088 Kazan, Russia Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center of RAS, Arbuzov Str. 8, 420088 Kazan, Russia Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center of RAS, Arbuzov Str. 8, 420088 Kazan, Russia Department of Inorganic Chemistry, Kazan National Research Technological University, K. Marx Str. 68, 420015 Kazan, RussiaInstitute of Physics of the Czech Academy of Sciences, Na Slovance 2, 182 21 Prague, Czech RepublicArbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center of RAS, Arbuzov Str. 8, 420088 Kazan, Russia Department of Physical Chemistry, Kazan (Volga Region) Federal University, Kremlyovskaya Str. 18, 420008 Kazan, RussiaArbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center of RAS, Arbuzov Str. 8, 420088 Kazan, Russia Zavoisky Physical-Technical Institute, FRC Kazan Scientific Center of RAS, Sibirsky Tract 10/7, 420029 Kazan, RussiaArbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center of RAS, Arbuzov Str. 8, 420088 Kazan, Russia Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center of RAS, Arbuzov Str. 8, 420088 Kazan, Russia Department of Inorganic Chemistry, Kazan National Research Technological University, K. Marx Str. 68, 420015 Kazan, RussiaArbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center of RAS, Arbuzov Str. 8, 420088 Kazan, Russia The present work introduces the series of thiacalix[4]arenes (H<sub>4</sub>L) bearing different upper-rim substituents (R = H, Br, NO<sub>2</sub>) for rational design of ligands providing an antenna-effect on the NIR Yb<sup>3+</sup>-centered luminescence of their Yb<sup>3+</sup> complexes. The unusual inclusive self-assembly of H<sub>3</sub>L<sup>−</sup> (Br) through Br<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mi mathvariant="sans-serif">π</mi></semantics></math></inline-formula> interactions is revealed through single-crystal XRD analysis. Thermodynamically favorable formation of dimeric complexes [2Yb<sup>3+</sup>:2HL<sup>3−</sup>] leads to efficient sensitizing of the Yb<sup>3+</sup> luminescence for H<sub>4</sub>L (Br, NO<sub>2</sub>), while poor sensitizing is observed for ligand H<sub>4</sub>L (H). X-ray analysis of the single crystal separated from the basified DMF solutions of YbCl<sub>3</sub> and H<sub>4</sub>L(NO<sub>2</sub>) has revealed the transformation of the dimeric complexes into [4Yb<sup>3+</sup>:2L<sup>4−</sup>] ones with a cubane-like cluster structure. The luminescence characteristics of the complexes in the solutions reveal the peculiar antenna effect of H<sub>4</sub>L(R = NO<sub>2</sub>), where the triplet level at 567 nm (17,637 cm<sup>−1</sup>) arisen from ILCT provides efficient sensitizing of the Yb<sup>3+</sup> luminescence.https://www.mdpi.com/1420-3049/27/20/6793calix[4]arenesYb<sup>3+</sup> complexesluminescencehalogen-bondingX-ray analysis |
| spellingShingle | Sergey N. Podyachev Svetlana N. Sudakova Rustem R. Zairov Victor V. Syakaev Alexey N. Masliy Michal Dusek Aidar T. Gubaidullin Alexey P. Dovzhenko Daina N. Buzyurova Dmitry V. Lapaev Gulnaz Sh. Mambetova Vasily M. Babaev Andrey M. Kuznetsov Asiya R. Mustafina Modulating the Inclusive and Coordinating Ability of Thiacalix[4]arene and Its Antenna Effect on Yb<sup>3</sup>-Luminescence via Upper-Rim Substitution<xref rid="fn+-20221012160304-1908848" ref-type="fn">+</xref> Molecules calix[4]arenes Yb<sup>3+</sup> complexes luminescence halogen-bonding X-ray analysis |
| title | Modulating the Inclusive and Coordinating Ability of Thiacalix[4]arene and Its Antenna Effect on Yb<sup>3</sup>-Luminescence via Upper-Rim Substitution<xref rid="fn+-20221012160304-1908848" ref-type="fn">+</xref> |
| title_full | Modulating the Inclusive and Coordinating Ability of Thiacalix[4]arene and Its Antenna Effect on Yb<sup>3</sup>-Luminescence via Upper-Rim Substitution<xref rid="fn+-20221012160304-1908848" ref-type="fn">+</xref> |
| title_fullStr | Modulating the Inclusive and Coordinating Ability of Thiacalix[4]arene and Its Antenna Effect on Yb<sup>3</sup>-Luminescence via Upper-Rim Substitution<xref rid="fn+-20221012160304-1908848" ref-type="fn">+</xref> |
| title_full_unstemmed | Modulating the Inclusive and Coordinating Ability of Thiacalix[4]arene and Its Antenna Effect on Yb<sup>3</sup>-Luminescence via Upper-Rim Substitution<xref rid="fn+-20221012160304-1908848" ref-type="fn">+</xref> |
| title_short | Modulating the Inclusive and Coordinating Ability of Thiacalix[4]arene and Its Antenna Effect on Yb<sup>3</sup>-Luminescence via Upper-Rim Substitution<xref rid="fn+-20221012160304-1908848" ref-type="fn">+</xref> |
| title_sort | modulating the inclusive and coordinating ability of thiacalix 4 arene and its antenna effect on yb sup 3 sup luminescence via upper rim substitution xref rid fn 20221012160304 1908848 ref type fn xref |
| topic | calix[4]arenes Yb<sup>3+</sup> complexes luminescence halogen-bonding X-ray analysis |
| url | https://www.mdpi.com/1420-3049/27/20/6793 |
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