Oxyethylated Fluoresceine—(thia)calix[4]arene Conjugates: Synthesis and Visible-Light Photoredox Catalysis in Water–Organic Media
Fluorescent derivatives attract the attention of researchers for their use as sensors, photocatalysts and for the creation of functional materials. In order to create amphiphilic fluorescent derivatives of calixarenes, a fluorescein derivative containing oligoethylene glycol and propargyl groups was...
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| Format: | Article |
| Language: | English |
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MDPI AG
2022-12-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/28/1/261 |
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| author | Vladimir Burilov Aigul Fatykhova Diana Mironova Elza Sultanova Ramil Nugmanov Alina Artemenko Anastasia Volodina Amina Daminova Vladimir Evtugyn Svetlana Solovieva Igor Antipin |
| author_facet | Vladimir Burilov Aigul Fatykhova Diana Mironova Elza Sultanova Ramil Nugmanov Alina Artemenko Anastasia Volodina Amina Daminova Vladimir Evtugyn Svetlana Solovieva Igor Antipin |
| author_sort | Vladimir Burilov |
| collection | DOAJ |
| description | Fluorescent derivatives attract the attention of researchers for their use as sensors, photocatalysts and for the creation of functional materials. In order to create amphiphilic fluorescent derivatives of calixarenes, a fluorescein derivative containing oligoethylene glycol and propargyl groups was obtained. The resulting fluorescein derivative was introduced into three different (thia)calix[4]arene azide derivatives. For all synthesized compounds, the luminescence quantum yields have been established in different solvents. Using UV-visible spectroscopy, dynamic light scattering, as well as transmission and confocal microscopy, aggregation of macrocycles was studied. It was evaluated that calixarene derivatives with alkyl substituents form spherical aggregates, while symmetrical tetrafluorescein-containing thiacalix[4]arene forms extended worm-like aggregates. The macrocycle containing tetradecyl fragments was found to be the most efficient in photoredox ipso-oxidation of phenylboronic acid. In addition, it was shown that in a number of different electron donors (NEt<sub>3</sub>, DABCO and iPr<sub>2</sub>EtN), the photoredox ipso-oxidation proceeds best with triethylamine. It has been shown that a low molecular weight surfactant Triton-X100 can also improve the photocatalytic abilities of an oligoethylene glycol fluorescein derivative, thus showing the importance of a combination of micellar and photoredox catalysis. |
| first_indexed | 2024-03-09T09:45:02Z |
| format | Article |
| id | doaj.art-b4bc3a00d5324c9d86f209a5573d2c4c |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-09T09:45:02Z |
| publishDate | 2022-12-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-b4bc3a00d5324c9d86f209a5573d2c4c2023-12-02T00:41:46ZengMDPI AGMolecules1420-30492022-12-0128126110.3390/molecules28010261Oxyethylated Fluoresceine—(thia)calix[4]arene Conjugates: Synthesis and Visible-Light Photoredox Catalysis in Water–Organic MediaVladimir Burilov0Aigul Fatykhova1Diana Mironova2Elza Sultanova3Ramil Nugmanov4Alina Artemenko5Anastasia Volodina6Amina Daminova7Vladimir Evtugyn8Svetlana Solovieva9Igor Antipin10Alexander Butlerov Institute of Chemistry, Kazan Federal University, 18 Kremlevskaya St., 420008 Kazan, RussiaAlexander Butlerov Institute of Chemistry, Kazan Federal University, 18 Kremlevskaya St., 420008 Kazan, RussiaAlexander Butlerov Institute of Chemistry, Kazan Federal University, 18 Kremlevskaya St., 420008 Kazan, RussiaAlexander Butlerov Institute of Chemistry, Kazan Federal University, 18 Kremlevskaya St., 420008 Kazan, RussiaAlexander Butlerov Institute of Chemistry, Kazan Federal University, 18 Kremlevskaya St., 420008 Kazan, RussiaAlexander Butlerov Institute of Chemistry, Kazan Federal University, 18 Kremlevskaya St., 420008 Kazan, RussiaAlexander Butlerov Institute of Chemistry, Kazan Federal University, 18 Kremlevskaya St., 420008 Kazan, RussiaInterdisciplinary Center for Analytical Microscopy, Kazan Federal University, 18 Kremlevskaya St., 420008 Kazan, RussiaInterdisciplinary Center for Analytical Microscopy, Kazan Federal University, 18 Kremlevskaya St., 420008 Kazan, RussiaArbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center of RAS, 8 Arbuzov Str., 420088 Kazan, RussiaAlexander Butlerov Institute of Chemistry, Kazan Federal University, 18 Kremlevskaya St., 420008 Kazan, RussiaFluorescent derivatives attract the attention of researchers for their use as sensors, photocatalysts and for the creation of functional materials. In order to create amphiphilic fluorescent derivatives of calixarenes, a fluorescein derivative containing oligoethylene glycol and propargyl groups was obtained. The resulting fluorescein derivative was introduced into three different (thia)calix[4]arene azide derivatives. For all synthesized compounds, the luminescence quantum yields have been established in different solvents. Using UV-visible spectroscopy, dynamic light scattering, as well as transmission and confocal microscopy, aggregation of macrocycles was studied. It was evaluated that calixarene derivatives with alkyl substituents form spherical aggregates, while symmetrical tetrafluorescein-containing thiacalix[4]arene forms extended worm-like aggregates. The macrocycle containing tetradecyl fragments was found to be the most efficient in photoredox ipso-oxidation of phenylboronic acid. In addition, it was shown that in a number of different electron donors (NEt<sub>3</sub>, DABCO and iPr<sub>2</sub>EtN), the photoredox ipso-oxidation proceeds best with triethylamine. It has been shown that a low molecular weight surfactant Triton-X100 can also improve the photocatalytic abilities of an oligoethylene glycol fluorescein derivative, thus showing the importance of a combination of micellar and photoredox catalysis.https://www.mdpi.com/1420-3049/28/1/261calixarenethiacalixarenefluoresceinluminescenceclick chemistryphotoredox catalysis |
| spellingShingle | Vladimir Burilov Aigul Fatykhova Diana Mironova Elza Sultanova Ramil Nugmanov Alina Artemenko Anastasia Volodina Amina Daminova Vladimir Evtugyn Svetlana Solovieva Igor Antipin Oxyethylated Fluoresceine—(thia)calix[4]arene Conjugates: Synthesis and Visible-Light Photoredox Catalysis in Water–Organic Media Molecules calixarene thiacalixarene fluorescein luminescence click chemistry photoredox catalysis |
| title | Oxyethylated Fluoresceine—(thia)calix[4]arene Conjugates: Synthesis and Visible-Light Photoredox Catalysis in Water–Organic Media |
| title_full | Oxyethylated Fluoresceine—(thia)calix[4]arene Conjugates: Synthesis and Visible-Light Photoredox Catalysis in Water–Organic Media |
| title_fullStr | Oxyethylated Fluoresceine—(thia)calix[4]arene Conjugates: Synthesis and Visible-Light Photoredox Catalysis in Water–Organic Media |
| title_full_unstemmed | Oxyethylated Fluoresceine—(thia)calix[4]arene Conjugates: Synthesis and Visible-Light Photoredox Catalysis in Water–Organic Media |
| title_short | Oxyethylated Fluoresceine—(thia)calix[4]arene Conjugates: Synthesis and Visible-Light Photoredox Catalysis in Water–Organic Media |
| title_sort | oxyethylated fluoresceine thia calix 4 arene conjugates synthesis and visible light photoredox catalysis in water organic media |
| topic | calixarene thiacalixarene fluorescein luminescence click chemistry photoredox catalysis |
| url | https://www.mdpi.com/1420-3049/28/1/261 |
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